DE2112027A1 - Chloroprene polymer containing a dispersible form of magnesia - Google Patents

Description

Merck & Co., Inc.
Rahway New Jersey / USA

Chlorine containing a dispersible form of magnesia

prenpolymeres

The present invention relates to improvements in the manufacture of rubber materials. In particular, befnPt this invention relates to an improved form of magnesium oxide for use in regulating so-called "scorch" · and curing rate of ITeoprene rubber formulations. In addition, the MgO material of the invention results in Production of neoprene vulcanizates of excellent quality.

Neoprene is the general term applied to the synthetic group riastoraerer based on the polymers of chloroprene (2-chloro-1,3-butadiene) is used. To the group of neoprene formulations for general purposes generally belong to two classes modified with sulfur (e.g. Neoprene type G) and which are not modified with sulfur (both

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109841/1635

14277.

Spielsv / ice neoprene type W). It should be noted that that this invention applies to all types of chloroprene polymers which for example by polymerization in the presence of mercaptans or other modifying agents (chain transfer agents), such as dialkylxanthogen disulfides, or in the presence of sulfur be produced, followed by plasticization, or the very limited polymerized without agents, to which the removal of the unconverted chloroprene monomer occurs is applicable. All of these methods are extensively described in the literature. See, for example, the U.S. Patents 1,950,436, 2,227,517, 2,234,215, and 2,567,117, Neoprene GKA is an example of a G-type neoprene. This special neoprene and its manufacturing process is on pages 769-771 in "Synthetic Rubber", published by G.S. Whitby, (John Wiley and Sons Inc. (1954)).

The chloroprene polymers used are both polychloroprene themselves as well as mixtures containing a chloroprene polymer. Also are both those used with chloroprene polymers Materials such as antioxidants, plasticizers, IT hardeners, Accelerators, retarders, reinforcing agents, pigments and fillers, well known as the amounts under various Circumstances should be used.

The use of MgO in the manufacture of heoprene compounds is well known. The mechanism by which MgO promotes the vulcanization process is not entirely understandable; but the influence it exerts is recently in Whitby's "Synthetic." Rubber "(1954) on pages 775-776 (John I ^ iley) v.'orden, according to which between the procedural security and curing rate equilibrates when the MgO is combined with other oxides such as zinc oxide. the Use of zinc oxide as the only hardening agent leads to both rapid hardening as well as an even hardening

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came about with extensive vulcanization, ie such materials are "flat curing". The limits of such compounds lie in their pronounced tendency to be "scorchy" 2U or consist in premature hardening of the system. In addition, the hardening approximates to a relatively low point. The use of magnesia as the sole hardening agent leads to neoprene compounds that harden very slowly and are safe to manufacture, but where hardening activity tends to persist. In addition to ^{Figure 1} , magnesium oxide improves vulcanization aging properties by probably acting as an acceptor for the tiny amounts of hydrogen chloride released from the neoprene during manufacture, curing, and vulcanization aging. Zinc oxide and magnesium oxide, combined with one another, complement each other and lead to well-balanced materials, the properties of which - often advantageous - can be varied by adjusting the ratio of one oxide to the other.

It is the purpose of the invention to be a highly reactive MgO preparation for neoprene manufacturing that is quick and easy dispersed evenly into the neoprene. The MgO dispersions of the invention yield - when used in the manufacture of neoprene uses v / earth - an improved Mooney-Scorch-Echutz (originally and after aging of the non-vulcanized connection) and provide improved manufacturing and storage security made of non-vulcanized neoprene. Furthermore has the dispersion does not have an adverse effect on the vulcanizate properties of neoprene.

This results in less waste and allows greater latitude and flexibility in manufacture and Storage of the non-vulcanized neoprene. This highly active, easily dispersible MgO formulation consists of magnesium oxide and at least one surface-active M:;. < eel and / or

a metal soap and at least one rubber plasticizer.

MgO is currently used in both powder and specially dispersed form in the manufacture of neoprene. However, the HgO dispersions of the invention run on manufacture of products with improved performance in terms of Mooney Scorch protection (original and after aging) in addition, if they are used with the MgO preparations that are currently used in the rubber industry. The MgO dispersions of the invention can be used in both liquid and solid states in the manufacture of neoprene. The dispersions can be supplied to the neoprene manufacturer, for example, in the form of a paste, in the form of rods, blocks or beads etc., so that the dispersions can be appropriately used in the manufacture of neoprene. The particular form of the MgO dispersion is a matter of choice and can be determined using those well known to those skilled in the art conventional methods.

It is known in the industry that MgO - when it is atmospheric Exposure to moisture and carbon dioxide - quickly converts to carbonate or hydroxide. Neither magnesium carbonate However, magnesium hydroxide is still used in neoprene vulcanization effective in the way that MgO is effective. Accordingly, it must always be ensured that the for use MqO preparation specific to meoprene production does not suffer a loss of activity. Another advantage of the dispersions of the invention relates to their ability to Maintain the activity of the MgO for substantial storage periods without taking precautions imposed by the industry usually, faces.

The invention contemplates the use of the "neoprene qualities"

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of MgO which is precipitated and calcined after the precipitation v / earth. Except for these lightly calcined, highly surface-active ones Forms of MgO can also use less active types of MgO in practicing the invention will. The class of less active MgO materials includes highly calcined types of MgO.

The amount of surfactant to use and / or the metallic soap is not critical and highly effective preparation agents can be made using 2.5-50 parts by weight of this Materials per 100 parts by weight of MgO can be obtained. The preferred range can be from 5-15 parts by weight per 100 parts by weight MgO fluctuate. It should be noted that the system has only a single surfactant or mixtures of may contain surfactants or just a metallic soap or mixtures of metallic soaps.

In addition, representatives of both material classes can be combined with one another to obtain the effective amount of surface-active Means and / or to obtain metal soap. In other words, the amount of surfactant and metallic soap can be vary in the range of 0-100% in relation to the other component.

The amount of MgO surfactant / metallic soap to use and rubber plasticizer in the manufacture of neoprene usually varies between about 2-16 parts by weight per hundred Parts by weight rubber. This includes systems in which MgO is used as a production material with and without the presence other metal oxides is used. For most applications, the recommended amount is 4 parts by weight per 100 parts by weight Rubber.

In practicing the invention, a plasticizer is used for rubber in combination with the MgO and the upper

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surfactants and / or the metal soap used. the The amount of plasticizer to be used is not critical and can vary between about 5-70 parts by weight per 100 parts by weight of MgO. It should be mentioned that the system has either a single plasticizer or mixtures of different plasticizers may contain.

The particular rubber plasticizer that can be used in practicing this invention is not critical and includes those plasticizers which are well known and commonly used for these purposes by those skilled in the art of rubber uses v / earth. See Morton "Introduction to Rubber Technology", pages 151-171, Reinhold Publ. Comp. (1964); Murray and Thompson "The Neoprens", pages 39-41, Du Pont (1963). This class includes:

Petroleum oils such as paraffinic, naphthenic, and aromatic. Resin, waxes and asphalt derived from petroleum can also belong to this class. This also includes mineral oils, Esters such as esters of organic alcohols and polybasic acids; Resins and polymers such as aromatic hydrocarbon resins and liquid elastomers (such as polyisobutylene and polybutene), oils, pitch, and resins made from pine and coal tar be won; natural fats and oils (vegetable oils, blown oils and fatty acids).

Coumarone-indene resins (aromatic and aliphatic hydrocarbon resins, derived from coal and petroleum) [Resins in Rubber, Gardner L. P.rown, Pennsylvania Industrial Chemical Corp. (1969), p. 104J.

As a representative representative of the petroleum, paraffinic petroleum like Cyclolube 2310 (Golden Bear Oil Co.), naphthenic oils such as Shellflex 371 (Shell Chemical Company) and Cyclolube 138 (Golden Pear Oil Co.) and aromatic oils,

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ORIGINAL INSPECTED

such as Bearflex LPO (Golden Bear Oil Co.) and Califlux 550 (Golden Pear Oil Co.) point out. The esters are exemplified by butyl leate, dibutyl phthalate and tricresyl phosphate, dioctyl sebacate, trioctyl phosphate and triethylene glycol caprylate. Examples of the resins and polymers are Kenflex N, (aromatic hydrocarbon) P.RC-22, Para-Flux, Vistanex LM-HIJ (a non-colored polyisobutylene with an average viscosity molecular weight (according to Staudinger) of 10,000 - 11 700) and the Flosbrenes Fluid SBR polymers, which are liquid, or liquid mixed polymers of styrene and butadiene, which contain around 25% styrene building blocks. In this class, Flosbrene 25 MV, which has a molecular weight of about 5,000 and a viscosity in poise of 4,500 (25 ° C) and 550 (45 ° C), is of particular interest _Φ \ JFhe Flosbrenes Fluid SBR Polymeres, AG Susie and FJ Sackfield, American Synthetic Rubber Corp. 3. Examples of coumarone-indene resins known to be used in the practice of the invention are the picco resins, which belong to a group of polyindene or coumarone-indene resins which are derived from petroleum. Of particular interest are Picco 6100-1-1 / 2 and Piccotex 100 (a ct-methylstyrene-vinyltoluene mixed polymer with an oil ratio of oil-methylstyrene to vinyltoluene of 1: 3). [^ Resins in Rubber, earlier, pages 72-75, 86 and Product Data Sheet 079 of Pennsylvania Chemical Corp., page 6 ^. Examples of vegetable oils that can be used in compounding chloroprene polymers are linseed oil, rapeseed oil, and safflower oil.

The polybutenes are a number of synthetic hydrocarbons polymers produced by catalytic polymerization of straight chain and branched butenes can be obtained. They are weakly colored liquids of low to high viscosity and Stickiness.

Typical examples from the class of practical

Polybutenes which can be used to carry out the invention are the so-called Oronite polybutenes. [New Improved Oronite Polybutenes (1963), California Chemical Corp. ^. Polybutene is of particular interest No. 128.

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O I. to OO I. T! cn

ι S.

PHYSICAL PROPERTIES Test Method No. 6 No. 8 No. 16 No. 18 No. 20

Condition visual clear, bright and free of debris or

suspended material

Color, Gardner ASTM D-1544 11111

spec. Weight at 60 / 15.6 ° C ASTM D-287 0.846 0.862 0.880 0.888 0.891

average Molecular weight

Mechrolab Osmometer SM-180-6 330 440 640 730 800

Molecular Weight Disperse Index ...... SM-180-6 - 1.0

Viscosity at 37.8 ° C, SSU ASTM D-445

& D-446 134 560 5 700 9 500 16 500

Viscosity at 98.9 ° C, SSU ASTM D-445

& D-446 41 63 250 350 · 550

Viscosity index ASTM D-567 66 87 96 103 105

Flash Point, ° C ASTM D-92 132.2 137.8 168.3 168.3 187.7

Focus, ⁰ C ASTM D-92 146.1 160.0 198.9 212.8 221.1

Pour point, ⁰ C "ASTM D-97 -51.1 -34.4 -23.3 -15.0 -12.2

Loss b. Heating,% (5 hours,

at 162.8 ° C) ASTM D-6 - 7.6 -

Thermal expansion coefficient

per ⁰ C (15-1OO ° C) SM-15-23 0.00079 0.00078 0.00074 0.00072 0.00072

CHEMICAL PROPERTIES

Prom number, g / 100 g SM-20-28 44 37 26 24 22

Neutralization value, mg KOH / g ... ASTM D-664 0.01 0.01 0.01 0.01 0.01

organic chloride as chlorine,% by weight ... SM-205-12 0.007 0.004 0.003 0.003 0.003

anora. Chlorides and sulfates ASTM D-878 germ none < no no <- no *

Table (continued ) Test method

Total sulfur content,% .... ASTM D-1552

Carbon residue,% ASTM D-189

Water content, ppm ASTM D-1533

r. 6th No. 8 No. 16 No. 18 No. 20 £> » -4 0.01 0.01 0.01 0.01 0.01 no no no no no 40 40 40 40 40

ω ti m

Table (For ts nuation.)

PHYSICAL PROPERTIES Test Method No. 24 No. 32X No. 32 No. 122 No. 128 λ

Condition visual clear, bright and free of debris or;

suspended material

Color, Gardner ASTM D-1544 11 1 1 1

spec. Weight at 60 / 15.6 ° C ASTM D-287 0.898 0.905 0.908 0.915 Ο, 9Ϊ7

average Molecular weight

Mechrolab Osmometer SM-180-6 950 1 260 1 400 2 500 2 700

Molecular Weight Disperse Index SM-180-6 1.5 1.6 1.8-2.3

Viscosity at 37.8 ° C, SSU ASTM D-445

& D-446 40,000 104,000 123,000 715,000 890,000

Viscosity at 98.9 ° C, SSU. ASTM D-445

& D-446 1 050 2 460 2 990 15 800 19 500

Viscosity index ASTM D-567 112 116 118 '122 122 ^

Flash Point, ⁰ C ASTM D-92 204.4 251.6 223.9 260 265.5

Focus, ⁰ C ASTM D-92 243.3 293.3 271.1 318.3 323.9

Pour point, ° C ASTM D-97 -6.7 1.7 4.4 12.8 18.3

Loss b. Heating,% (5 hours,

at 162.8 ° C) ASTM D-6 1.0 0.3 0.4 - 0.1

Thermal expansion coefficient

per ⁰ C (15 - 100 ° C) SM-15-23 0.00070 0.00067 0.00066 0.00063 0.00062

CHEMICAL PROPERTIES

Prom number, g / 100 g,. . SM-20-28 18 14 13 8 7 - *

Neutralization value, mg KOH / g ... ASTM D-664 0.01 0.01 0.01 0.01 0.01 J ^ J

ore.Chloride as chlorine, wt% ... SM-205-12 0.003 0.003 0.003 0.002 0.002 ; ^:}

anorcr. Chlorides and sulfates ASTM D-878 no no no no no. no ~ --3

Table (continued) Test method

Total sulfur content,% ASTM D-1552

Carbon residue,% ASTM D-18 9

Water content, ppm ASTM D-1533

r. 24 No. 32X No. 32 No. 122 No. 128 «T “J 0.01 0.01 Ρ, οι 0.01 0.01 • »J no no no no no 40 40 40 40 40

14277

As would be shown above, in the practice of the invention, in addition to a single representative, mixtures of several Plasticizer used v / earth. It has been found that desirable results are obtained using genes especially if one of the representatives of the plasticizer mixture is either a liquid elastomer such as polyisobutylene, Polybutene, or the flosbrenes or a coumarone-indene resin, such as Picco 6100-1-1 / 2 or Piccotex 100. The addition of the above plasticizers to the MgO dispersions improves the mixing and extrusion properties the dispersion without impairing the dispersion performance in the neoprene. When the liquid elastomers and coumarone-indene resins are used in combination with other plasticizers, 0.4-20 parts by weight per 100 parts by weight MgO can be used.

The properties of typical petroleum used as plasticizers are the following:

Shellflex 3 71

Viscosity, SSü / 37.8 ^P C '420

Viscosity, SSU / 98.9 ° C 53.1

Weight, ⁰ API 26.1 Specific Weight / 15.6 ° C 0.8978

kg / 3.78 liters 7.476

Color, ASTM 10.5

Flash Point, C 215.6

Pour point, ⁰ C -31.7 volatility, 22 hrs / 10 7.2 ° C wt% 0.62

Neutralization No. mg KOH / g 0.03

Distillation, ⁰ C

IBP 376.7

5 % 396.1

10% 402.8

5O% 432.2

90% 462.8

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Shellflex 371 (continued) ο, -

Aniline point,

UV absorption at 260 mu

Viscosity-weight constant . Refractive index / 20 C refraction section

Molecular analysis, clay gel, wt% asphalt

Polar compounds Aromatic hydrocarbons Saturated hydrocarbons

Carbon atom analysis,% aromatic carbon atoms, C. Naphthenic C atoms, C Paraffinic C atoms, C

ASTM Rubber Extending Oil Type 98.3 0.9 0.840 1.4890 1.0423

0.3 15.5 84.2

44

54

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cn
ι

Specific gravity, 15.6 C ⁰ API weight paint, ASTM D-1500

Viscosity, SUS at 37.8 ⁰ C

Viscosity, SUS at 98.9 ° C o "

Pour point,
Flash point,
Focus,

COC ⁰ C COC ° C

Aniline point, C total aniline point, C mean. Molecular weight Refractive index, 20 ° c

Molecular analysis,

ASTM D-2006 (Rostler) asphalt

Nitrogen bases 1. Acid derivatives 2. Acid derivatives

Paraffins

Aromatic gel

CALIFLUX

1.0217 7.0

D8.0

313,000

475

32.2 240.6 268.3

35.5 435

1.5843

none 31 "22 38 9 91

BEARFLEX LPO

0.9679
14.7

2.0

138

0.9573
16.3

2,500

CYCLOLUBE

4053
0.9053
24.8

3.0

539

2310

0.9236 21.7

3.0

1430

38.1 86.3 56.6 78.9 -37.2 9.4 -28.9 -12.2 154.4 218.3 204.4 223.9 187.8 243.3 235.0 260.0 15.0 70.0 95.6 90.6 255 411 436 410 1.5422 1.5294 1.4936 1.5043 no no no no 2 10 1 2 17th 14th 4th 9 63 37 26th 33 18th 39 69 56 82 61 31 44

m cc on

continuation CALIFLUX 550 28 BEARFLEX LPO . . _Q CYCLOLUBE
. ¹ I ⁸ Δηκτ no 2310 t- Molecular analysis,
ASTM D-2007 (clay gel)
Asphalt none 63 no no 1 no N) polar connections 9 3 10 26th 2 aromatic 0.04 77 50 73 40. saturated -1146 20th 40 0.04 58 ' Neutralization no. 0.9667 0.03 0.04 43 0.03 Viscosity index 1.0748 -104 -56 0.8426 18th Viscosity weight
constant . 54
7th 0.9520 0.9020 1.0444 0.8653 Refraction section
ndM 39 1.0548 1.0526 6th
40 1.0463 ^{% C} N 3.81 38
34 23
37 54 10 · ■
43 % c _p 28 40 3.40 47 kg / 3.78 liters 3.63 3.60 3.50

m σ

ro

D.

The properties of typical mineral oils / known as plasticizers are the following:

Soez. Weight Saybolt Kinematic Engler Viscosity ASTM. Flash point quality at 15.5 ° C viscosity viscosity __o "_ _Λ ο-, pour point no. At 378O _C ( _i S ^) ² ^^ ' ^ **' * ^coc

at 37.8 ° C ° C ⁰ C

- »350 USP 0.880 / 0.895 345/355 74/77 32.0 5.6 -23 -23.3 221.1 ο

Ο3 85 NF 0.845 / 0360 80/90 15/18 5.0 2.0 - 7 -6.7 187.8

IO

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PICCOTEX

Softening point, ball and ring color, Gardner scale (max.) Specific weight kg / 3.78 liters, solid resin

Gardner viscosity, in toluene at 25 ° C

Acid number, less than saponification number, less than Bromine number (electrometric), less than ash, less than

Refractive index at 25 ° C ozone number

Flash point, ⁰ C Focal point, C

PICCO 6100-1-1 / 2

Petroleum hydrocarbon resin (produced by homo- and mixed polymerisation of dienes and olefins aliphatic, alicyclic and monobenzonoid aryl alkene types of distillates of cracked petroleum materials).

Paint, coal tar, max. I 1/2

* Melting point, 100 ° C

Specific weight l, O6

Bromine number ^ Tr. (electrometric) 10.3

Iodine number (corrected) 16.4

Refractive index, 25 ° C 1.60

Flash point, COC ° C 480

Acid number, max. I.

Saponification no., Max. I.

100 Q at 1 ⁰ C 1 1 1 1 , 04 8th 0 , 67 1 70% solids
stop 0 262 298 ,1 % , 583 ,8th , 9

Ball and Ring Method

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OfcONÄL INSPECTED

Representative examples of metallic soaps or fatty acid esters of metals falling within the scope of the present invention, are stearates, oleates, paltnitate, ricinoleates and octoates of calcium, aluminum, magnesium and iron. Other metals, that can be used are zinc, cadmium, barium, ele, sodium, potassium, lithium and nickel. Preferred examples of Metal soaps are magnesium stearate, calcium stearate, aluminum stearate, Iron distearate and iron tristearate.

The surfactants falling within the scope of this invention are either non-ionic or ionic or mixtures thereof. As examples of classes of well-known materials the following can be specified:

Non-ionic agents

Mono- and diglycerides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, Polyoxyethylene sorbitol ester, polyoxy. ethylene acids, fatty alcohols, polyethylene glycols, KonylphenoxypolySthylenoxyäthanole, Fatty acid esters of: glycerol, ethylene glycol, di- and polyethylene glycol, propylene glycol, tetraester of pentaerythritol and fatty acids, modified polyvinylpyrrolidone, like Ganex V polymers, modified low molecular weight polyethylene (like Epolene).

Ionic agents alkylarylsulfonates

It should be noted that the selection of a particular surfactant is not critical to practical use The invention is practiced as long as it is either non-ionic or ionic and does not interfere with keoprene vulcanization.

Representative surfactants are as follows:

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ORIGINAL iNSPECTEP

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Name of the connection

Great

Non-ionic agents

Span 40, sorbitan monopalmitate Span 80, sorbitan monooleate Span 85, sorbitan trioleate Tween 20, polyoxyethylene (20) Tween 40, polyoxyethylene (20) Tween 60, polyoxyethylene (20) Tween 80, polyoxyethylene (20)

Renex 20, polyoxyethylene ester of mixed fatty and resin acids

Tergitol NPX
Tergitol 15-S-9

Emulphor VN-430
Igepal CO-430

Glycerol monstearate glycerol tristearate Pentaerythritol tetrastearate

Cetyl stearyl alcohol Carbowax 4000
Epolene E-14

Ganex V-216

Atlas G-33OO

Sorbitan fatty acid ester Sorbitan fatty acid ester Sorbitan fatty acid ester

j polyoxy

Sorbitan monolaurate

_{Sorbitan monopalmitate} , .... Ί

^ ) ethylene-

Sorbitan monostearate) sorbitan

) fatty acid esters

Sorbitan monooleate

Polyoxyethylene acids nonylphenyl polyglycol ether straight-chain alcohol polyglyco lathe ir

polyoxyethylated fatty acid

Nonylphenoxy polyethyleneoxyethanol

Fatty acid esters of glycerol Fatty acid esters of glycerol

Tetraesters of pentaerythritol and fatty acids

Fatty alcohol
Polyethylene glycol Modified low molecular weight polyethylene

Modified polyvinylpyrrolidone

Ionic means

Alkyl aryl sulfonate

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For other non-ionic and ionic designs Means that can be used in practicing the invention are referred to publications such as "General Characteristics of Atlas Surfactants" (1963) and "Detergents and Emulsifiers" (1969) Annual, edited by John W. McCutcheon, pointed out.

Representative examples of combinations of surfactants Means, with and without metallic soaps, are the following: (The preferred ratio of the components is shown in brackets)

Span 80 / Tween 60 (50/50) (

Span 80 / Tween 80 (60/40)

Span 80 / Tween 80 / ethylene glycol monostearate (25/25/50) Span 80 / Tween 80 / glycerol monostearate (40/30/30) Span 80 / Tween 80 / Epolene E-14 (20/15/65) Span 80 / Tween 80 / calcium stearate (40/30/30) Span 80 / Tween 80 / Carbowax 4000 (40/30/30) Span 80 / calcium stearate (60/40)
Span 80 / aluminum stearate (60/40)
Igepal CO-43O / calcium stearate (67/33)
Igepal CO-430 / aluminum stearate (67/33)

Although the exact reason for the greatly improved results achieved by the MgO dispersions of the invention is not fully understood, it is believed that the beneficial effects are due to: a) Increase in the penetration of the MgO particles by reducing the interfacial dimension at the interfacial area of MgO and plasticizer. The advantages of this are: faster wetting of the MgO during the preparation of the dispersion and the possibility of obtaining a higher solids content (or a lower viscosity with the same solids content).

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ORIGINAL INSPECTED

b) Increase in performance (an original Mooney scorch and bin age stability when the dispersions are used in neoprene. It is believed, that this can be attributed to a reduction in the interfacial tension at the interface between MgO and neoprene rubber which makes the MgO more reactive.

The MgO dispersions of the invention can be prepared using methods well known to those skilled in the art can be prepared. One effective method is to disperse the MgO by using forceps Mix into the dispersing medium. Mix with strong shear forces is welcome. The dispersion can be made at room temperature, but higher temperatures (80 - 120 ° C) preferred. It should be noted that by reducing the particle size of MgO (before, after or during manufacture the dispersion) the dispersion performance is improved.

All dispersions used in the following examples were prepared in a double-armed sigma blade mixer. Of the Mixer had a processing capacity of 2.6 5 liters and was provided with a jacket for steam heating. The dispersions were prepared by adding all of the ingredients except MgO and mixing with heating until one Temperature of 100-1O5 ° C has been reached; then the MgO was added and mixing continued at 100-105 ° C until a complete wetting of the MgO by the dispersing medium had taken place.

The neoprene compounding was carried out on a two roll laboratory rubber mill carried out. The rubber mill had a front roll and a rear roll, each with a diameter of 15.24 cm and a length of 33.02 cm. The front roll was running at 24 RPM and the back roll was running at 33.6 RPM. A 7.5 PF motor was used to power the mill. The composition

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^{: "R"} NSPSCTED

¹⁴²⁷⁷ j $ 21 ^: 27

The neoprene rubber used in the following examples was as follows:

Neoprene rubber chuk

Neoprene GNA 100 parts

Stearic acid 0.5

MgO powder or MgO dispersion as shown

SRF soot 29

NeozoneA (N-phenyl-cL-naphthylamine,

Antioxidants). 2

ZnO 5

The rubber was processed into a belt on the front roller of the laboratory mill and processing continued on the mill, until the tape was smooth and free of holes. Then stearic acid, MgO (as a powder or as a dispersion), carbon black, NeoEone A and -ZnO added. Each ingredient became uniform and added to the rollers at a constant rate and taken up by the mixture before the next ingredient is added After mixing, the batch was removed from the mill, weighed and put back into the mill. The rollers were set at a distance of 0.762 mm. The material was put into the mill 6 times. During the milling process, water at a temperature of 20 ° C. was passed through the rollers. The material was then removed from the mill in a thin layer.

Mooney Scorch performance was measured on a Monsanto Mooney Rheometer at 127 C using a *
ASTM test method D-1646-63 determined.

meter at 127 ° C using a small rotor according to the

The MgO "neoprene quality" used in the following examples is Maglite D Kr. 3231, a lightly calcined magnesium oxide with a high surface activity, manufactured by Merck & Co., Inc. It has the following typical properties!

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ORtQtNAL INSPECTED

14277

Chemical Analysis Magnesium Oxide (MgO) Ignition Loss Carbon Dioxide (CO ₂ ) Bound Water (H ₉ O) Calcium Oxide (CaO) Silicon _{Dioxide (SiO 2} ) Chloride (Cl) Sulphate (SO ₃ ) Iron Oxide (Fe ₉ O-) Aluminum Oxide (Al ₃ O- ) Manganese (Mn)
Copper (Cu)
Acid insolubles

2m

-'Ui

typically 93.10% 4.86 0.46 4.40 0.79 0.27 0.17 0.68 0.03 0.10 0.0017 0.0002 0.05

Physical analysis

Appearance

Refractive Index Specific Weight Weight per 3.78 liters bulk weight (loose)

Sieve analysis

typical

clear, white, odorless powder 1.64 3.32 1.27 kg pcf

through a sieve with a mesh size of 0.14 8 mm through a sieve with a clear mesh size Mesh size of 0.074 mm through a sieve with a mesh size of 0.044 mm

Mean Main particle size, determined with the

Electron microscope 0.05 micron distribution 0.10 micron 0 0.15 micron 0.05 - 0.20 micron 0.10 - 0.25 micron 0.15 - 0.20 -

IOO%%

99.5% 0.086 microns

20.9%

48.8

20.2

7.1

3.0

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109841/1635 ORfOMAL

14277 '211

Surface 185 m ² / g

Iodine number 135

example 1 Performance evaluation of the dispersion

MgO dispersions (Haglite D) in a white oil (Ramol-85) were made using various amounts of surfactant Medium chip 80 manufactured.

Increasing amounts of chip 80 lead to an increase in MgO wetting, as shown by differences in consistency.

Dispersion mixture consistency at room temperature

(% By weight) peratur

Maglite D mineral oil 50 50 • 50 47.5 50 42.5 50 37.5

Chip 80

0 very dry, crumbly paste

2.5 very dry, crumbly paste

7.5 soft paste

12.5 semi-liquid paste

These dispersions were first compounded into a neoprene rubber formulation given above using a laboratory mill. They were used in amounts of 4 parts by weight per 100 parts by weight of rubber. For comparison, Maglite D powder was ^{compounded in the same V 7} and used in amounts of 4 parts by weight per 100 parts by weight and 2 parts by weight per 100 parts by weight. With 2 parts by weight of powder per 100 parts by weight of rubber, the same amount of Maglite D is added to the neoprene as with 4 parts by weight per 100 parts of rubber of the 50% Maglite D dispersions.

The performance of the dispersions and powder additives to the neoprene compound was judged by Mooney Scorch t, times, t .. is

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109841/1635 ν- - ORIGINAL INSPECTED

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2V.

the time required for Mooney viscosity to rise 10 units above the minimum. The t, _Q times for the original Mooney scorch should desirably be relatively long (similar to those resulting from the use of Maglite D powder in amounts of 4 parts by weight per 100 parts by weight of rubber). The unvulcanized compounds were first aged for 6 days at 50 ° C. and then the Mooney viscosity t. -Time determined. Dip t. - Desirably, time should change little during aging during storage (bin aging). If the t. -The times of the original connections or those that have aged during storage are short, the rubber processor does not have enough time to make and vulcanise his connections. That leads to waste. Relatively high t times reduce the losses caused by waste and allow less critical conditions for the production and storage of non-vulcanized neoprene compounds.

Example 2

The following 50% dispersions were used in amounts of 4 parts per 100 parts of rubber in neoprene:

(A) dispersion mixture (C wt .-%) "

Original Moorey-Scorch protection and Mooney-Fcorch protection in the event of exposure to aging t ₁ time (in minutes)

Maglite D mineral oil

Chip 80 originally after 6 days

at 50 ° C

(a) 50 50 5 0 5 42 (b) 50 47, 5 2, 5 45 (C) 50 42, 5 7, 5 44 (d) 50 37, 12, 45

23 30 35 38

Maglite D powder was given on similar Feise in the Concentrations used:

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ORIGINAL INSPECTED

14277

(B) Maglite D (parts by weight per

100 Gev7.-parts rubber)

Original Mooney Scorch Protection and Mooney Scorch Protection with aging in storage t, time (in minutes)

originally after 6 days at 50 ^° C

4 2

40
34

35 23

A comparison of the Mooney scorch protection of the above dispersion mixtures of the invention (A) (b-d), which are 2 parts by weight per 100 parts by weight Rubber (or 4 parts by weight χ 50% per 100 parts by weight of rubber) Maglite D and Maglite-D powder (B) contain in amounts of 2 parts by weight per 100 parts by weight of rubber clearly shows the beneficial effects produced by the dispersions according to the invention be achieved. The dispersion of the invention containing 2 parts by weight per 100 parts by weight of Maglite D (A) (d) rubber is actual clearly superior to the previous Maglite D powder in quantities of 4 parts by weight per 100 parts by weight of rubber. It should It should also be noted that the dispersion mixtures of the invention (A) (b-d) are much better than the previous Maglite D dispersion in mineral oil (A) (a).

Similar results were achieved with the above stated, if other MgO dispersions are within the scope of the Invention like the following iir, in view of their ability against To protect "scorch" were tested:

1 Q 9 8 Λ;

UNAL INSPECTED

Dispersion mixture (wt .-%)

Maglite D plasticizer

surfactant or metal soap

Consistency at room temperature

O CD CO P-

09

50

50 50

Mineral oil (Ramol-85) (50%)

Mineral oil (Ramol-85) (42.5%)

Petroleum, aromatics (Bearflex-LPO) (4 5%)

Epolene E-14 (7.5%)

Renex 20 (5%)
Atlas G33OO (5%)
Glycerol monostearate (5%)
Igepal CO-430 (5%)
Ganex V-216 (5%)
Fmulphor VN-430 (5%)
Ethylene glycol monostearate (5%)
Cetostearyl alcohol (5%)
Span 80 (5%)
Span 80 (5%)

(Bearflex-LPO) (32%) Iron (III) distearate (8%)

50 (45%) 50 (45%) 50 (45%) 50 (45%) 50 (45%) 50 Kenflex N (45%) 50 Butyl oleate (45%) 50 Dibutyl phthalate (45%) 50 Tricresyl phosphate (45%) 60 Petroleum, aromatics

very dry, crumbly paste

soft paste

soft paste very soft paste soft paste semi-liquid paste soft paste very v / oak paste soft paste stiff paste soft paste soft paste

soft paste

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13th 2 '■ 1: ":" ■: 7

The beneficial effects on the Mooney scorch, both on the original as well as those after storage aging are illustrated by representative dispersions of the invention. the Tests were conducted according to the dispersion performance evaluation discussed above.

Dispersion Mixture Original Mooney Scorch

(Wt .-%) Protection and Mooney Scorch

Protection against aging in storage t. -Time (in minutes)

Maglite D plasticizer surface - originally after 6 days

active agent at 50 ° C

50 mineral oil

(Ramol-85) Epolene E-14

(42.5 %) (7.5%) 43

50 petroleum, aromatics

(Eearflex-LPO) Atlas G-33OO

(45%) (5%) 42

50 "" "glycerol mono-

stearate (5%) 39 32

50 "" "Emulphor VN-430

(5%) 42 32

50 Kenflex N (45%) ethylene glycol

monostearate (5%) 44 31

The following is a representative prior MgO dispersion with a Maglite D dispersion within the scope of the invention compared.

The previous dispersion, which used aliphatic materials as a dispersion medium for the MgO, was soft-plastic. the Maglite D dispersion had the following composition: Maglite D 52.9%

Petroleum, naphthenic

(Shellflex 371) 43.3

Span 80 2.4

Calcium stearate 1.4

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109841/1635 ; <, ;;.?. :; V- - i "&# ORIGINAL INSPECTED

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2 * " S.

Each dispersion was compounded into the neoprene formulation in amounts of 4 parts by weight per 100 parts by weight of rubber and mixed in a laboratory internal mixer (Banbury, Type 00) which had a processing capacity of 2,000 ril. The performance of the dispersions was _{assessed according to Mooney Scorch t 1} times.

Original Mooney Scorch Protection and Moone.y Fcorch Protection at storage age, time (in minutes)

originally after 6 days

at 50 ° C

previous dispersion 36

Maglite D Dispersion 45

This experiment clearly shows that the MgO dispersions of the invention are superior to previous dispersions.

Other examples of representative formulations that can be used in practicing the invention include are the following:

Dispersion formulations n % by weight

(a) MgO 53.0 Shellflex 371 43.2 Calcium stearate 1.4 Sorbitannonooleate 2.4

(b) MgO 55 Shellflex 371 40 Pentaerythritol tetrastearate 5

(c) MgO 55 Cyclolube 2310 40 sorbitan monooleate 5

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10 9 8 41/16 3 5 f & T ^ mWi i% - ν% ORJQINAL INSPECTED

14277 ₉ j _o , -

continuation Dispersion formulation Gev; .-%

(d) MgO 55 Shellflex 371 40 pentaerythritol tetrastearate 2.5 Nonylphenoxypolyethyleneoxyethanol 2.5

(e) MgO 55 Shellflex 371 30 iron distearate or iron tristearate 15

With the above formulations, very desirable results will be obtained obtained when 2 parts by weight of oil by 2 parts by weight of coumarone-indene resin (for example Piccotex 100 or Picco 6100-1-1 / 2) or 2 parts by weight of a liquid elastomer (for example Vistanex LM-MS).

for example 'IgO 53.0

Shellflex 371 41.2

Piccotex 100 2.0

Aluminum stearate 1.4

Polyoxyethylene sorbitan monooleate 2 ', 4

Preparation of the McrQ Dispersion in Rod Shape After the dispersion was prepared by high shear mixing, the hot dispersion was extruded in a hot extruder. The extruded rod was then cut to the desired lengths and allowed to cool to room temperature.

Preparation of the MgO dispersion in the form of spheres Spheres are prepared by adding the hot dispersing medium to the powder while slowly mixing at about 100 ° C. Just enough dispersing medium was added to bind the particles together.

- 31

0 η ^r - '. w

Claims (1)

Claims 1. Containing a dispersible form of magnesia Chloroprene polymer, characterized in that it contains MgO and at least one surface-active agent and / or at least contains a metal soap and at least one rubber plasticizer. 2. Chloroprene polymer according to claim 1, characterized in that that it contains about 2-16 parts by weight of a dispersible form of MgO per 100 parts by weight of polymer that the total amount of surface-active agent and metal soap about 2.5 to 50 parts by weight, based on 100 parts by weight of MgO, and the The amount of rubber plasticizer is about 5-70 parts by weight, based on 100 parts by weight of MgO. 3. chloroprene polymer according to claim 2, characterized in that that the surfactant is a non-ionic. 4. chloroprene polymer according to claim 2, characterized in that the surfactant is an ionic. 5. Chloroprene polymer according to claim 3, characterized in that the nonionic surface-active agent is mono- and diglycerides and / or sorbitan fatty acid esters and / or polyoxyethylene sorbitan fatty acid esters and / or polyoxyethylene sorbitan esters and / or polyoxyethylene acids and / or fatty alcohols and / or polyethylene glycols or nonylene glycols and / or polyethyleneoxyethanols and / or fatty acid esters of glycerol,. Ethylene glycol _r Di- and polyethylene glycol or propylene glycol and / or modified polyvinylpyrrolidone and / or modified low molecular weight polyethylene and / or tetraester of Pentaerythritol and fatty acids are. - 32 - 109841/16 3 6 6. chloroprene polymer according to claim 5, characterized in that the non-ionic surface-active agent is sorbitan fatty acid ester and / or polyoxyethylene sorbitan fatty acid ester and / or nonylphenoxypolyäthylenoxyäthanole and / or tetraester of Pentaerythritol and fatty acids are. 7. chloroprene polymer according to claim 4, characterized in that that the ionic surfactant is an alkyl aryl sulfonate. 8. chloroprene polymer according to claim 2, characterized in that the metal soap is a stearate of calcium, aluminum, magnesium or iron. 9. chloroprene polymer according to claim 6, characterized in that the rubber plasticizer is a petroleum. 10. chloroprene polymer according to claim 9, characterized in that the rubber plasticizer is a naphthenic petroleum, the surfactant sorbitan monooleate; and the metallic soap Calcium stearate is. 11. A method for the use of MgO in the compounding and production of a chloroprene polymer, characterized in that that the improvement consists in the use of MgO in a dispersible form, the dispersion of MgO, at least a surfactant and / or at least one metallic soap and a rubber plasticizer. 12. The method according to claim 11, characterized in that the polymer is about 2-16 parts by weight of a dispersible form of MgO per 100 parts by weight of polymer contains that the total amount of surfactant and metal soap is about 2.5 - 50 parts by weight, based on 100 parts by weight of MgO, and the amount of rubber plasticizer about 5-70 parts by weight, based on 100 parts by weight of "qO," 109841/1635 J it amounts to. . _. : 13. The method according to claim 12, characterized in that the surfactant is a non-ionic. 14. The method according to claim 12, characterized in that the surfactant is an ionic. 15. The method according to claim 13, characterized in that the non-ionic surface-active agent is mono- and diglycerides and / or sorbitan fatty acid ester and / or polyoxyethylene sorbitan fatty acid ester and / or polyoxyethylene sorbitol ester and / or polyoxyethylene acids and / or fatty alcohols and / or Polyethylene glycols and / or Konylphenoxypolyäthylenoxyäthanole and / or fatty acid esters of glycerine, ethylene glycol, . Di- and polyethylene glycol or propylene glycol and / or modified polyvinylpyrrolidone and / or modified low molecular weight Are polyethylene and / or tetraesters of pentaerythritol and fatty acids. 16. The method according to claim 15, characterized in that the non-ionic surface-active agent is sorbitan fatty acid ester and / or polyoxyethylene sorbitan fatty acid ester and / or nonylphenoxypolyäthylenoxyäthanole and / or tetraester of Pentaerythritol and fatty acids are. 17. The method according to claim 14, characterized in that the ionic surfactant is an alkyl aryl sulfonate is. 18. The method according to claim 12, characterized in that the metal soap is a stearate of calcium, aluminum, magnesium or iron. - 34 - 109841/1635 19. The method according to claim 16, characterized in that the rubber softener is a petroleum. 20. The method according to claim 19, characterized in that the rubber plasticizer is a naphthenic petroleum that surfactants are sorbitan monooleate and the metal soap is calcium stearate. 21. Mixture for use in the compounding and production of neoprene, characterized in that it consists of a dispersible form of MgO and at least one surfactant and / or at least one metal soap and one Rubber plasticizer. 22. Mixture according to claim 21, characterized in that there is about 2-16 parts by weight of a dispersible form of MgO per 100 parts by weight of polymer contains that the total amount of surface-active Agent and metal soap about 2.5-50 parts by weight per 100 parts by weight of MgO, and the amount of rubber plasticizer about 5-70 parts by weight, based on 100 parts by weight of MgO. 23. Mixture according to claim 22, characterized in that the surface-active agent is a non-ionic. 24. Mixture according to claim 22, characterized in that the surface-active agent is an ionic. 25. Mixture according to claim 23, characterized in that the nonionic surface-active agent is mono- and diglycerides and / or sorbitan fatty acid ester and / or polyoxyethylene sorbitan fatty acid ester and / or polyoxyethylene sorbitol ester and / or polyoxyethylene acids and / or fatty alcohols and / or polyethyleneoxyethylene glycols and / or nonylphenoxyethylene / or fatty acid esters of glycerine, ethylene glycol _t di- - 3 ₅ 109841/1635 and polyethylene glycol or pronylene glycol and / or modified Polyvinylpyrrolidone and / or modified low molecular weight polyethylene and / or tetraesters of pentaerythritol and fatty acids are. 26. Mixture according to claim 25, characterized in that the non-ionic surface-active agent is sorbitan fatty acid ester and / or polyoxyethylene sorbitan fatty acid esters and / or nonylpherioxypolyethyleneoxyethanols and / or tetraesters of pentaerythritol and fatty acids. 27. Mixture according to claim 24, characterized in that the ionic surfactant is an alkyl aryl sulfonate. 28. Mixture according to claim 22, characterized in that the metal soap is a stearate of calcium, aluminum, magnesium or iron. 29. Mixture according to claim 26, characterized in that the rubber plasticizer is petroleum. 30. Geraisch according to claim 29, characterized in that the The rubber softener is a naphthenic petroleum, the surfactant sorbitan monooleate and the metal soap calcium stearate is. 31. Mixture according to claim 30, characterized in that it is in the form of rods or beads. Process for the production of a vulcanizable chloroprene polymer, characterized in that a dispersible form of MgO is added to a chloroprene polymer, wherein the dispersible form of MgO from MgO and at least one surfactant and / or at least one metal soap and a rubber plasticizer. - 36 - 109841/1635 "fa".. 14277 Jf 211 -J 77 33. The method according to claim 32, characterized in that the polymer contains about 2-16 parts by weight of a dispersible form of HgO per 100 parts by weight of polymer, that total of surfactant and metal soap about 2.5 to 50 parts by weight, based on 100 parts by weight of MgO, and the amount of Rubber plasticizer is about 5-70 parts by weight, based on 100 parts by weight of MgO. 34. "The method according to claim 33, characterized in that the surfactant is a non-ionic. 35. The method according to claim 33, characterized in that the surfactant is an ionic. 36. The method according to claim 34, characterized in that the non-ionic surface-active agent is mono- and diglycerides and / or sorbitan fatty acid ester and / or polyoxyethylene sorbitan fatty acid ester and / or polyoxyethylene sorbitol esters and / or polyoxyethylene acids and / or fatty alcohols and / or Polyethylene glycols and / or nonylphenoxypolyäthylenoxyäthanole and / or fatty acid esters of glycerine, ethylene glycol, Di- and polyethylene glycol or propylene glycol and / or modified polyvinylpyrrolidone and / or modified low molecular weight Are polyethylene and / or tetraesters of pentaerythritol and fatty acids. 37. The method according to claim 36, characterized in that the non-ionic surface-active agent is sorbitan fatty acid ester and / or polyoxyethylene sorbitan fatty acid esters and / or nonylphenoxypolyethyleneoxyethanols and / or tetraesters of pentaerythritol and fatty acids. - 37- 109841/1635 ORIGINAL INSPECTED 38. The method according to claim 35, characterized in that the surfactant is an alkyl aryl sulfonate. 39. The method according to claim 33, characterized in that the metal soap is a stearate of calcium, aluminum, magnesium or iron. 40. The method according to claim 36, characterized in that the rubber plasticizer is a petroleum. 41. The method according to claim 40, characterized in that the rubber plasticizer is a naphthenic petroleum, the surface-active Means sorbitan monooleate and the metal soap is calcium stearate. 42. Chloroprene polymer according to claim 9, characterized in that that the rubber plasticizer is a naphthenic petroleum and the surfactant is pentaerythritol tetrastearate. 43. The method according to claim 19, characterized in that the rubber plasticizer is a naphthenic petroleum and the surfactant is pentaerythritol tetrastearate. 44. Mixture according to claim 29, characterized in that the rubber plasticizer is a naphthenic petroleum and the surface-active Agent is pentaerythritol tetrastearate. 45. The method according to claim 40, characterized in that the rubber plasticizer is a naphthenic petroleum and the surface-active Agent is pentaerythritol tetrastearate. - 38 109841/1635