DE2004494A1 - - Google Patents

Description

Dr .-! Ng. Wooden houses

Dip!. · N4ct Goldbach

¹ Palen ta nw ä'te ^ January Ϊ9? Ο

OFFENBACH AM MAIN ^{yy /} Herrnstr. 37 - Tel. 88 56 42

INBESCOH

Joint stock company for industrial

! Research and radiation use

Schwerzenbaoh - Switzerland Schorenstrasse ~ "~~"

Process for the improvement of the radical formation that induced the polymerization catalysts Graft polymerization or graft copolymerization *.

tion

Induced by conventional radical-forming polymerization catalysts Graft polymerizations have a positive temperature coefficient for the reaction rate. Therefore, with increasing temperature, higher yields are obtained. It is but also known that some high polymers, such as z «£», are saturated Polyester only blackens itself at low temperatures let plug, even if the light-off temperature of the radical-forming polymerization catalyst at sioh deep enough to trigger graft polymerisationHie An? -

OO90SO / 2OOO

However, the use of high reaction temperatures has different effects Disadvantages and requires a great deal of technical effort

It has now been found that the reactivity of high polymers in graft polymerization induced by radical-forming polymerization catalysts such as organic peroxides or graft copolymerization can be increased significantly if in a specific for the corresponding high polymer Reaction temperature range is worked. This allows the reaction temperature to be lowered in many cases and at the same time reduce the formation of homopolymer.

The invention accordingly provides a process for improving the graft polymerization or graft copolymerization induced by radical-forming polymerization catalysts of one or more radically polymerizable compounds on substrates made of synthetic high polymers, which is characterized in that the substrate, the polymerizable β (n) compound (s) and the or the polymerization catalyst (s) and accelerators are brought to a reaction temperature which is in the temperature range of the glass transition of the high polymer forming the substrate

The method is suitable in the first Lini · for those Hooh-

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polymers, which are usually difficult at low temperatures j are to be grafted, such as saturated polyesters, especially j Polyethylene glycol terephthalate, optionally modified polyacrylonitrile or polyamides, such as, for example, polyhexamethylene adipamide (Polyamide 6.6), condensates of epsilon-aminocaproic acid (polyamide 6) or condensates of 11-aminoundecanoic acid (polyamide 11) whose glass transition areas are between 40 and 100 ° 0.

According to the literature, the most important synthetic The following glass transition temperature ranges for high polymers:

Polyester »65 to 85 ° G (1)

Polyamide-6,6: 4-5 to 65 ° G (2) Polyamide-6: - 4o to 6o ° 0 (3)

Polyacrylonitrile
, (pure, unmodified): 95 to 1o5 ° C (4)

The method according to the invention proceeds particularly favorably Grafts on substrates made of polyethylene glycol terephthalate, which is pronounced in the temperature range of the glass transition Has maximum.

The lowering of the reaction temperature in the inventive The process has the great advantage that the yield

0098 50/2 0 0 0.

be increased in graft polymer or graft copolymer

j can and at the same time the formation of homopolymer strongly j

is reduced. J

The high polymers can be in the form of films, textile fibers j

or yarns and textile fabrics such as woven fabrics, Ge j act, knitted or non-woven fabrics according to the invention

To be subjected to treatment. ;

The usual organic peroxides, such as methyl ethyl ketone peroxide, for example, can be used as radical-forming polymerization catalysts or dibenzoyl peroxide, salts of the transition metals, such as ammonium sulfate or nitrate and organic azo compounds such as azobisisobutyronitrile alone or in the presence of polymerization accelerators, e.g. organic heavy metal salts such as cobalt octonate or tertiary amines such as N.N.-dimethylaniline can be used.

The polymerization catalyst is advantageously chosen so that the light-off temperature is 1o to 2o ° below the temperature range the glass transition of the high polymer forming the substrate is to allow diffusion of the prior to the reaction allow compound to be polymerized in the substrate au

Polymerisable or copolymers as radical Gh; .able ver

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bonds come those with one or more polymerizable ones or copolymerizable double bonds into consideration, such as, if necessary substituted hydrocarbons, substituted activated double bonds containing carboxylic acids or dicarboxylic acids and their esters, optionally substituted alkynes, alkynecarboxylic acids

• - ■■■ '"■ ■ i

or alkynedicarboxylic acids and their esters, also vinyl or H. Allyl and acrylic monomers, especially vinyl-substituted ones aromatic or heterocyclic hydrocarbons; Vinyl esters, such as vinyl acetate and higher carboxylic acid vinyl esters, possibly Alkyl-substituted carboxylic acid vinyl esters containing sulfo groups; Vinyl ethers, such as optionally substituted alkyl, cycloalkyl or aryl vinyl ether; vinyl substituted silicones or vinyl silanes as well as vinyl sulfones; Diallyl fumarate; Diallyl maleates; allyl-substituted phosphates, phosphites or carbonates; Epoxy alkyl acrylates; alkyl-substituted alkyl, cycloalkyl · - or |

Aluminum acrylates; optionally alkyl-substituted hydroxyalkyl, hydroacyoyoalkyl or hydroxyarylacrylates; alkyl-substituted dial- * kylaminoalkylaoylatesj alkyl-substituted disiliconalkyl acrylates; unsaturated carboxylic acid, such as ltacon- | Malonic and Fuaarsätire as well as their esters or anhydrides j optionally alky-substituted acrylic acids. ₄ acrolein or acrylonitrile; possibly »alkyl-substituted acrylic amides or their N- ^ substituted derivatives *

This disconnection or misappropriation of the same can alone or in ^ egenwaa? t of solvents for diö radicaliach

merisable compound or swelling agents for the substrate are used · They can be in the form of solutions! Apply emulsions or suspensions to the substrate.

The method according to the invention is carried out expediently in such a way that the polymerizable compound (s) optionally in the presence of a suitable swelling agent or solvent together with the substrate and the radical-forming agent Polymerization catalyst optionally still in the presence of a polymerization accelerator above the light-off temperature of the The catalyst is heated to the temperature range of the glass transition of the high polymer forming the substrate and this reaction temperature for the entire duration of the graft polymerization is kept constant. The process can be carried out in the presence of air or, in certain cases, under oxygen-free conditions. Before heating to the reaction temperature, it can also be advantageous to modify the substrate and the polymerizable compound (s) if necessary. in the presence of a suitable swelling agent or solvent below the light-off temperature of the polymerization catalyst 1 to be stored for up to 24 hours in order to allow diffusion of the compound (s) to be polymerized into the substrate before the reaction «Possible.

Some embodiments of the invention are. based on

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Drawing explained in more detail · Figures 1 and 2 show diagrams on the, dependence of the graft yield and the homopolymerization on the reaction temperature.

example 1

A pre-cleaned fabric made of Polyäthylenglykolterephthalatfä- ^ the 75/75 denier, not heat-set, is placed in a glass vessel containing styrene. The liquor ratio is 1: 2o (1 part by weight of tissue to 20 parts by weight of solution). At 0 to 1o ° G 1 part of a commercial dibenzoyl peroxide as well 0.1 part of N.N-dimethylaniline added

The vessel with the tissue and the solution will open after 1 hour brought to a temperature of 80 ° C and this temperature constant jj for 2 hours with temporary slight cooling held. The tissue is now extracted thoroughly with toluene, to remove all homopolymer.

If the reaction temperature is varied between the values 6o and 130 ° C. under the conditions described, one obtains a Course of the increase in tissue density, as shown in FIG. 1 It is noticeable that the yield at 80 ° C has a significant maximum, which is more than 100% higher than the yield obtained at 130 °. Kick at 60 ° practically no graft polymerization. If you fall that

^e 00985Ö / 200 0 _BAD

Polystyrene also formed from the solution and determines gravimetrically the amount of polystyrene that has been formed per unit weight of the solution, so one obtains the Temperature dependence of homopolymerization, as shown in Figure 2 is shown

Example 2

A pre-cleaned fabric made from polyhexamethylene adipamide threads is placed in a glass vessel containing a solution of 9o parts by weight of styrene in 1o parts by weight of methanol. The liquor ratio is 1: 5o (1 part by weight of fabric to 50 parts by weight of solution) · 1 part by weight of methyl ethyl ketone peroxide and 0.1 part of oobalt octonate are added at room temperature · Then the vessel with the tissue and the solution is heated to 5o ° G and this temperature for 2 hours kept constant · The tissue is then extracted with toluene to constant weight · The increase in tissue weight is 10.2 percent.

Example 3

A 10% strength by weight aqueous solution of acrylic acid is placed in a glass vessel at ο to 10 ° G, which is 5 χ 10 ~ * mol / l Oerammon nitrate and nitric acid contains · In this solution a pre-cleaned «batiste fabric made of modified polyacrylonitrile is given. The liquor ratio is 1: 2oo

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(1 part by weight of tissue to 2oo parts by weight of solution). The vessel with the tissue and the solution is then warmed to 70 ° C for one hour while slowly passing through nitrogen. The tissue is then extracted with water until the weight is constant in order to remove all homopolymer.

Bibliography ·!

1) I. Goodman, JA Rhys-Pelyenters VeI. I, The Plastics Institute (1965)
U. Bianohi - Double Liaison 126, 177, (1966)

P.V. Paporo, R.O. Winckelhofer, R. J. Oswald-Rubber Chem. Teahnol ·, £ 8 * < >. 4, 999 - 1oo6 (1965)

2) R, S. Boyer, R. * S. Spencer - J. Appl. Phys. 1 ^ _x 598 (1944) LB Morgan J * Appl. Chem. 4 * 16o (195 ^) RE Boyer J. Appl. Pbys. 2 ^ _x 825 (1954)

3) MN Charon, WW Moseley Jr. - Tort. Res. J. 2 ^ _x 525 - 535I

(1959)

L. E. Nielsen. Mechanical Properties of Polymers, New York, Reinhold Publ., P. 21 (1962)

P. T. Papero, R. G. Winokelhofer, N. J. Oswald - Rubber Chem

Technol., ^ B _x No. 4, 999 - 1oo6 (1965) j

4) .JEnoyclopedia of Polymer Science and Technolegy ToI 7 » p. 461 (1967)

I. Groodman, -. The Royal Inst ot (3iemistry, Lecture Series No. 5, p 47 (1967).

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Claims (1)

Patent claims: "1.J Process for improving the graft polymerization induced by radical-forming polymerization catalysts or graft copolymerization of one or more free-radically polymerizable compounds onto substrates Synthetic hollow polymers, characterized in that the substrate, the polymerizable compound (s) and the or the polymerization catalyst (s) and accelerator are brought to a heating temperature which in the temperature range of the glass transition of the substrate forming high polymers 2.) Method according to claim 1, characterized in that the heating of the polymerizable compound (s) and the polymerization catalyst (s) and accelerator takes place under oxygen-free conditions 3 ·) Method according to claim 1 or 2, characterized in that as free-radically polymerizable or copolymerizable compounds those with one or more polymerizable or copolymerizable double bonds are used ^r ~~ 009850/2000 - 4.) Method according to one of claims 1 - 3, thereby characterized in that the polymerizable compound (s) in the presence of these solvent agents with the substrate be associated. 5.) Method according to one of the preceding claims, characterized in that the polymerizable compound (s) are brought into contact with the substrate in the presence of swelling agents, 6 #) method according to one of the preceding claims, characterized in that when using substrates made of saturated polyesters, polyamides and modified Polyacrylonitrile a reaction temperature in the range between 4o and 85 ° C is selected 7 ·) Process according to one of the preceding claims, characterized in that a radical-forming polymerization catalyst is used whose light-off temperature is 1o to 2o ° C below the temperature range of the glass transition of the high polymer forming the substrate is 8) Hit graft polymerisation or graft copolymers verse * henes substrate made of synthetic high polymers according to one of the preceding claims 009850/2000