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WO1992008764A1 - Composition elastomere - Google Patents

Composition elastomere Download PDF

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Publication number
WO1992008764A1
WO1992008764A1 PCT/US1991/008392 US9108392W WO9208764A1 WO 1992008764 A1 WO1992008764 A1 WO 1992008764A1 US 9108392 W US9108392 W US 9108392W WO 9208764 A1 WO9208764 A1 WO 9208764A1
Authority
WO
WIPO (PCT)
Prior art keywords
propylene
composition according
elastomer
butene
amorphous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1991/008392
Other languages
English (en)
Inventor
Richard Anthony Miller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of WO1992008764A1 publication Critical patent/WO1992008764A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • This invention relates to elastomeric compositions used in hot—melt formulations that contain an elastomer and an amorphous propylene copolymer.
  • Elastomeric compositions are well known and have been used in the industry for various applications such as adhesives, caulks, and sealants. These compositions typically contain an elastomer, a resin, and optionally a filler. The most costly component of these compositions is the elastomer. Therefore, compositions containing reduced amounts of elastomer to produce lower cost formulations would be very desirable and have been attempted in the industry. These lower cost formulations containing lower amounts of elastomer typically have increased filler loading or additional polymers such as low molecular weight polybutenes. However, these lower cost formulations typically have lower performance illustrated by low peel adhesion, tensile strength and/or poor weathering performance.
  • the present invention is directed to unique compositions containing an elastomer and an amorphous propylene copolymer selected from propylene/butene copolymers, and propylene/hexene copolymers. These compositions are useful in adhesive, caulk and sealant formulations and contain a reduced amount of elastomer while maintaining good performance. These compositions comprise: (a) about 10 to 90 wt.
  • % based on (a) plus (b) , of an amorphous propylene copolymer selected from copolymers of propylene/butene, propylene/hexene, and mixtures thereof, containing about 30 to 80 wt. % butene or hexene and about 70 to 20 wt. % propylene;
  • the amorphous propylene copolymer extends the elastomer, partially replacing the elastomer in the formulations while retaining and or improving performance properties such as enhanced peel adhesion and structural strength.
  • composition of the present invention comprises: (a) about 10 to 90 wt. %, based on (a) plus (b) , of an amorphous propylene copolymer selected from copolymers of propylene/butene, propylene/hexene, and mixtures thereof, containing about 30 to 80 wt. % butene or hexene and about 70 to 20 wt. % propylene; (b) about 10 to 90 wt.
  • compositions of the present invention are particularly useful in caulk and sealant formulations typically containing an elastomer, a resin, and filler.
  • the amorphous copolymers of propylene/butene and propylene/hexene are known and are generally prepared by anionic coordination polymerization. They are made in solution or in the melt phase at 160—200°C. These amorphous propylene copolymers are illustrated in the following U.S. patents 3,923,758, 4,826,939, 3,954,697, 4,072,813, and 4,259,470. The disclosures of which are incorporated herein in their entirety by reference. These amorphous propylene copolymers preferably contain between about 40 and 70 wt. % butene or hexene. More . preferably between about 45 and 55 wt. % butene or 40 and 50 wt.
  • the amorphous propylene copolymers can also be a propylene/butene/hexene terpolymers or contain minor amounts of monomers other than the butene or hexene.
  • This third monomer is preferably present in a concentration that is no more than about 20% by weight. Should the propylene copolymers contain a third monomer the amount of this third monomer is preferably between about .5 and 10% by weight. This third monomer is preferably ethylene.
  • the amorphous propylene copolymers are preferably maleated amorphous propylene copolymers preferably having an acid number between about 23 and 44. These maleated amorphous propylene copolymers are well known in the art and are prepared by graft polymerization as illustrated in U. S. 4,567,223 the disclosure of which is incorporated in its entirety herein by reference. The maleated amorphous propylene copolymers more preferably have an acid number between about 20 and 23. This aspect is disclosed and claimed more broadly in an application by the same inventor filed the same day as the present application.
  • the composition according to the present invention preferably contains about 25 to 75 wt. % amorphous propylene copolymer based on a total of copolymer and elastomer. More preferably the composition contains between about 40 and 60 wt. % amorphous propylene copolymer with about 50 wt. % amorphous propylene copolymer being most preferred.
  • composition according to the present invention when used as a hot—melt adhesive formulation, preferably contains about 20 to 70 wt. % tackifier more preferably about 40 to 60 wt. %.
  • the composition of the present invention when used as a caulk or sealant, preferably contains about 5 to 30 wt.. % tackifier, and about 20 to 60 wt. % filler. More preferably the caulk or sealant composition contains about 10 to 20 wt. % tackifier and about 20 to 30 wt. % filler.
  • the tackifier used in the composition of the present invention is preferably selected from at least one of the groups consisting of hydrocarbon resins, synthetic polyterpenes, and rosin esters.
  • the tackifier preferably has a ring and ball softening point of about 95 to 135°C.
  • Suitable resins and rosin esters are the terpene polymers having the suitable ring and ball softening point such as the polymeric, resinous materials including the dimers as well as higher polymers obtained by polymerization and/or copolymerization of terpene hydrocarbons such as the alicyclic, monocyclic, and bicyclic monoterpenes and their mixtures, including allo—ocimene, carene, isomerized pinene, pinene, dipentene, terpinene, terpinolene, limonene, turpentine, a terpene cut or fraction, and various other terpenes.
  • Particularly useful starting materials are terpene mixtures containing a mixture of sulphate terpene, and at least 20% of at least one other terpene selected from the group consisting of pinene, limonene, or dipentene.
  • the more preferred tackifying resins are selected from hydrocarbon resins such as disclosed in U.S.
  • hydrocarbon resins preferably have a ring and ball softening point of about 100 to 130°C, an acid number of about 0 to 2 an acid value of less than about 1 and an iodine value of 75 to 100.
  • hydrocarbon tackifying resins can be prepared by the polymerization of monomers consisting primarily of olefins and diolefins and include, for example, the residual by—product monomers resulting from the manufacture of isoprene.
  • Fillers suitable for use in the present invention are, for example, finely divided fume silica, calcium carbonate, titanium dioxide, zinc dioxide, graphite, clay, talc, other metal oxides, and the like. Such fillers have a particle size not much greater than 20 microns preferably between about 5 and 10 microns and are preferably selected from calcium carbonate, titanium dioxide, and zinc dioxide.
  • the elastomer used in the elastomeric composition of the present invention is selected from butyl elastomers, at least partially crosslinked butyl elastomers, styrene, ethylene/butadiene/styrene block copolymers and mixtures thereof. These elastomers are generally known and are prepared commercially. Elastomers are more preferably selected from butyl elastomers at least partially crosslinked with divinyl benzene and butyl elastomers having unsaturated isoprene and isobutylene units. Suitable elastomers for example include KALAR 5214 a partially crosslinked butyl elastomer from Hardman Chemical Company and EXXON 268 a crosslinked butyl elastomer from Exxon Chemical Company.
  • Antioxidants can also be added to the adhesive composition of the present invention.
  • effective antioxidants include, tris(di—t—butyl—p- hydroxybenzyl)—trimethylbenzene (available as Ionox 330 from Shell Chemical) , alkylated bisphenol (available as Naugawhite from Uniroyal) , zinc dibutyl dithiocarbamate (available as Butyl Zimate from R. T.
  • Vanderbilt and 4,4'—methylene bis(2,6-di—tert—butylphenol) (Ethyl 702) , tetrakis[methylene(3,5—di-tert—buty1-4— hydroxyhydroinnamate)methane] (available as Irganox 1010 from Ciba Geigy) , lauryl stearyl thiodipropionate (Plastanox 1212), and dilauryl 3,3'—thiodipropionate (Plastanox LTDP) , and 2,6-di-tert—butyl-p—cresol (BHT) .
  • the following examples are presented to further illustrate the present invention and are not intended to limit the reasonable scope thereof.
  • Test specimens for determining elevated temperature and elevated temperature shear strengths were prepared and tested according to shear strength — ASTM D—1002. Structural strength was determined from peel and tensile strength according to peel strength — ASTM D— 1876 and tensile strength — ASTM D-638.
  • Acid number expressed as milligrams of potassium hydroxide required to neutralize one gram of sample was determined in hot toluene using phenolthaline as indicator.
  • Example l This examples illustrates improvements in tensile strength of a sealant by substituting a propylene copolymer of the present invention for a portion of the elastomer. The only variance were the amount of elastomer and copolymer. The results in improvement in tensile strength are illustrated in the table below.
  • Example 2 The following example illustrates the preparation of a control elastomeric composition.
  • Polybutene H—100 34 Percent This formulation was compounded in a double arm jacketed mixer at 350°F for two hours. The formulation was then tested by peel adhesion, using a standard peel adhesion testing method commonly incorporated in the trade. The peel adhesions were prepared by applying a 20 mil film of the above sealant to an aluminum, cold roll steel, galvanized and glass substrates. The specimens were tested after standing for 24—hours at room temperature and then after water immersion for 21— ays at room temperature. The samples were tested on an Instron tester typically used in the sealant trade. This above formulation was then incorporated as a control in further testing and is indicated by A in Table 3 below.
  • Example 3 The formulations below were prepared and tested as above in Example 2 with the variations listed in the table. Table 3 below illustrates that the addition of an amorphous propylene—butene copolymer to an elastomeric composition, particularly the maleated copolymer, does not lower the properties and, in fact, enhances the peel strength of this sealant or caulk formulation, particularly the higher acid number maleated propylene—butene copolymer. All peel adhesion failures were cohesive.
  • Example 4 The formulations below were prepared and tested as above in Example 2 with the variations listed in the table. Table 4 below illustrates that the addition of a maleated terpolymer to an elastomeric composition does not lower the properties and in fact enhances the peel strength of the elastomeric composition over an unextended standard. All peel adhesion failures were cohesive. Table 4 Testing Formulation Percent/Weight
  • Example 5 The formulations below were prepared and tested as above in Example 2 with the variations listed in the table. Table 5 below illustrates that the addition of maleated propylene—ethylene copolymer, particularly the higher acid number of 43, does not lower the properties and in fact enhances the peel adhesion of the elastomeric composition, both initial and after 21—day water immersion over an unextended standard and nonmaleated amorphous polyolefin propylene—ethylene copolymer. The non—maleated amorphous copolymer was also better than the standard. All peel adhesion failures were cohesive.
  • Example 6 The formulations below were prepared and tested as above in Example 2 with the variations listed in the table. Table 6 below illustrates that the addition of maleated amorphous propylene—hexene copolymer to an elastomeric composition does not lower the properties and in fact enhances the peel strength of the elastomeric composition, both initial and after 21 day water immersion, over an unextended standard and a nonmaleated amorphous propylene—hexene copolymer containing sealant formulation.
  • the amorphous propylene—hexene copolymer extended the elastomer and did not significantly reduce the properties of the elastomeric composition, particularly for the initial peel adhesion. All peel adhesion failures were cohesive.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition élastomère renfermant un copolymère amorphe de propène sélectionné parmi les copolymères de butène de propène et de hexène de propène, ainsi qu'un élastomère sélectionné parmi les élastomères butyliques, les élastomères butyliques réticulés et les copolymères bloc styrène-éthylène-butadiène-styrène.
PCT/US1991/008392 1990-11-16 1991-11-15 Composition elastomere Ceased WO1992008764A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US61574290A 1990-11-16 1990-11-16
US615,742 1990-11-16

Publications (1)

Publication Number Publication Date
WO1992008764A1 true WO1992008764A1 (fr) 1992-05-29

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ID=24466634

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/008392 Ceased WO1992008764A1 (fr) 1990-11-16 1991-11-15 Composition elastomere

Country Status (1)

Country Link
WO (1) WO1992008764A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994003549A1 (fr) * 1992-07-31 1994-02-17 Eastman Chemical Company Composition elastomere contenant un elastomere et un copolymere de propylene/hexene amorphe
US6184290B1 (en) 1994-06-01 2001-02-06 The Dow Chemical Company Block copolymer compositions containing substantially inert thermoelastic extenders
US6218470B1 (en) 1994-06-01 2001-04-17 The Dow Chemical Company Thermoplastic elastomeric blends
US6403710B1 (en) 1994-08-29 2002-06-11 The Dow Chemical Company Block copolymer compositions containing substantially inert thermoelastic extenders
WO2006018246A1 (fr) * 2004-08-16 2006-02-23 Isocoll Chemie Gmbh Procede pour fixer un serpentin sur la platine d'un appareil frigorifique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850858A (en) * 1973-09-28 1974-11-26 Eastman Kodak Co Hot melt pressure sensitive adhesives
US4259470A (en) * 1979-08-30 1981-03-31 Eastman Kodak Company Propylene/1-butene or 1-pentene/higher 1-olefin copolymers useful as pressure-sensitive hot-melt adhesives
EP0285430A2 (fr) * 1987-04-03 1988-10-05 Minnesota Mining And Manufacturing Company Adhésif applicable à la chaleur à base de polypropylène amorphe
US4857594A (en) * 1988-04-28 1989-08-15 Baychem International, Inc. Melt adhesive compositions
EP0391697A2 (fr) * 1989-04-04 1990-10-10 Exxon Chemical Patents Inc. Elastomères butyliques résistant à l'ozone

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850858A (en) * 1973-09-28 1974-11-26 Eastman Kodak Co Hot melt pressure sensitive adhesives
US4259470A (en) * 1979-08-30 1981-03-31 Eastman Kodak Company Propylene/1-butene or 1-pentene/higher 1-olefin copolymers useful as pressure-sensitive hot-melt adhesives
EP0285430A2 (fr) * 1987-04-03 1988-10-05 Minnesota Mining And Manufacturing Company Adhésif applicable à la chaleur à base de polypropylène amorphe
US4857594A (en) * 1988-04-28 1989-08-15 Baychem International, Inc. Melt adhesive compositions
EP0391697A2 (fr) * 1989-04-04 1990-10-10 Exxon Chemical Patents Inc. Elastomères butyliques résistant à l'ozone

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994003549A1 (fr) * 1992-07-31 1994-02-17 Eastman Chemical Company Composition elastomere contenant un elastomere et un copolymere de propylene/hexene amorphe
US5330829A (en) * 1992-07-31 1994-07-19 Eastman Chemical Company Elastomeric composition containing elastomer and amorphous propylene/hexene copolymer
EP0652915A1 (fr) * 1992-07-31 1995-05-17 Eastman Chem Co Composition elastomere contenant un elastomere et un copolymere de propylene/hexene amorphe.
US6184290B1 (en) 1994-06-01 2001-02-06 The Dow Chemical Company Block copolymer compositions containing substantially inert thermoelastic extenders
US6184291B1 (en) 1994-06-01 2001-02-06 The Dow Chemical Company Block copolymer compositions containing substantially inert thermoelastic extenders
US6218470B1 (en) 1994-06-01 2001-04-17 The Dow Chemical Company Thermoplastic elastomeric blends
US6369161B1 (en) 1994-06-01 2002-04-09 The Dow Chemical Company Thermoplastic elastomeric blends
US6403710B1 (en) 1994-08-29 2002-06-11 The Dow Chemical Company Block copolymer compositions containing substantially inert thermoelastic extenders
WO2006018246A1 (fr) * 2004-08-16 2006-02-23 Isocoll Chemie Gmbh Procede pour fixer un serpentin sur la platine d'un appareil frigorifique

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