US 5,026,807 AGrant
Novel Ester Group-Containing (Meth)acrylic Acid Ester, Novel (Co)polymer Thereof, Composition Comprising the (Co)polymer and Composition Comprising the Ester Group Containing (Meth)acrylic Acid Ester
Issue Date:1991-06-25
•10 Claims
•5 Drawing Sheets
Abstract
A novel ester group-containing (meth)acrylic acid ester represented by the general formula (I): ##STR1## wherein R.sup.1 is a hydrogen atom or a methyl group, R.sup.2 is a C.sub.3-20 alkylene group, R.sup.3 is a C.sub.1-20 hydrocarbon group or its derivative, and l is an integer of 1-20, and a (co)polymer composed of said ester group-containing (meth)acrylic acid ester and other monomer(s) copolymerizable therewith. This (co)polymer gives a crosslinked product superior in heat resistance, low-temperature resistance and oil resistance.
Metadata
Assignee
- Japan Synthetic Rubber Co., Ltd.
Inventors
- Yosihiro Ohira
- Toshio Ohhara
- Toshio Miyabayashi
Application Information
Application Number:US 5231809
Filing Date:1990-05-15
Priority Date:1988-10-31
Art Unit:155
Classifications
IPC:
C08F 2210
Field of Search:
526321;320;324;325
Patent Drawings (5 sheets)
Description
This invention is explained more specifically below referring to Examples. However, this invention is not restricted to these Examples.
In the Examples, parts and % are by weight unless otherwise specified.
In the Examples, the properties of the (meth)acrylic acid esters (I), the (co)polymers thereof and the vulcanized products of said (co)polymers were measured according to the following test methods:
Infrared spectrophotometric analysis
Apparatus: A-III infrared spectrophotometer manufactured by Nihon Bunko K.K.
The infrared spectrophotometric analysis of a (meth)acrylic acid ester (I) was effected according to a coating method, and that of a (co)polymer thereof was effected according to a KBr tablet method.
NMR analysis
Apparatus: FX 100 .sup.13 C-NMR manufactured by NEC Corp.
A polymer was dissolved in chloroform and measured for .sup.13 C-NMR spectrum. The assignment of the peak(s) of the spectrum obtained was made based on Chemical Shift Ranges in Carbon-13 NMR Spectroscopy (Wolfgang Bremser Burghard Franke Hans Wagner).
Determination of amount of vinyl chloroacetate
This was made by determining the chlorine content of a polymer according to fluorescent X-ray analysis.
Determination of amount of allyl glycidyl ether
This was made by dissolving a polymer in chloroform and then determining its epoxy equivalent according to an acetic acid method.
Determination of amounts of vinyl acrylate and dihydrodicyclopentadienyloxyethyl acrylate
This was made by dissolving a polymer in chloroform and then determining its iodine value according to iodometry.
Elementary analysis
Apparatus: CHN-CORDER-MF3 manufactured by Yanagimoto Seisakusho K.K.
A sample was burnt in air at 950.degree. C. for 5 minutes and the composition of carbon atoms and hydrogen atoms was determined.
Intrinsic viscosity
Apparatus: Constant temperature water bath
A polymer was dissolved in chloroform and then measured for viscosity using an Ubbellohde viscometer.
Acid value
A sample was dissolved in ethyl alcohol and measured for acid value by neutralization titration.
Properties of vulcanized rubber
A rubber sheet was prepared from a rubber composition comprising the (meth)acrylic acid ester (I) or a rubber composition comprising a (co)polymer of the (meth)acrylic acid ester (I). The rubber sheet was then crosslinked by a crosslinking press for a given period of time and, if necessary, further crosslinked by a Geer oven for a given period of time.
The resulting vulcanized sheet or block was subjected to molding by Dumbbell cutter and measured for heat resistance, low-temperature resistance and oil resistance according to JIS K 6301.
EXAMPLE 1
(Preparation of novel acrylic acid ester)
In a flask provided with a stirrer and a Dean-Starke water separator were placed 300 g of an unsaturated carboxylic acid having the following structural formula (M-5300, a product of TOAGOSEI CHEMICAL INDUSTRY CO., LTD.)
(n is 1-5), 138 g of ethyl alcohol, 1 cc of concentrated sulfuric acid and 300 cc of toluene.
The resulting mixture was refluxed with heating and the water generated was separated from the water separator. Heating was continued until the generation of water was no longer seen. The reaction mixture was allowed to cool to room temperature. Then, the reaction mixture in the flask was washed with 500 cc of water, 500 cc of 1% sodium hydrogen-carbonate and 500 cc of water in this order, followed by drying with anhydrous sodium sulfate. Unreacted ethyl alcohol and toluene were removed by distillation under reduced pressure to obtain a colorless viscous, liquid product in a 80% yield. This product is named as novel acrylic acid ester (1).
The structure of this novel acrylic acid ester (1) was confirmed as follows.
The unsaturated carboxylic acid used as a material and the novel acrylic acid ester (1) were measured for acid value. As a result, the unsaturated carboxylic acid had an acid value of 190 mg KOH/g and the novel acrylic acid ester (1) had an acid value of 0.5 mg KOH/g.
Next, the infrared absorption spectrum of the novel acrylic acid ester (1) is shown in FIG. 1. The elementary analysis of the novel acrylic acid ester (1) gave a carbon content of 62.2% and a hydrogen content of 8.5%.
From the results of the acid values, the infrared absorption spectrum and the elementary analysis, the novel acrylic acid ester (1) was judged to be represented by the following formula:
EXAMPLE 2
(Preparation of novel acrylic acid ester)
The same procedure as in Example 1 was repeated, except that 387 g of 2-ethylhexyl alcohol was used in place of the ethyl alcohol, to obtain a colorless viscous liquid product in a 78% yield. This product was named as novel acrylic acid ester (2). The structure of this ester was confirmed in the same manner as in Example 1.
From the results of the acid values, the infrared absorption spectrum and the elementary analysis, the novel acrylic acid ester (2) was judged to be represented by the following formula:
EXAMPLE 3
(Preparation of novel acrylic acid ester copolymer and composition comprising said copolymer)
Into an autoclave purged with nitrogen were charged 100 parts of a monomer mixture, 4 parts of sodium laurylsulfate, 0.25 part of p-menthane hydroperoxide, 0.01 part of ferrous sulfate, 0.025 part of sodium ethylenediaminetetraacetate and 0.04 part of sodium formaldehyde sulfoxylate. The resulting mixture was subjected to reaction at 30.degree. C. until the conversion of the monomers reached 90%. Then, 0.5 part of N,N-diethylhydroxylamine was added to terminate the reaction.
The reaction mixture was taken out, and steam was blown thereinto to remove the unreacted monomers. The resulting rubber latex was added to a 0.25% aqueous calcium chloride solution for coagulation. The coagulation product was washed with water thoroughly and dried at about 90.degree. C. for 3 hours to obtain a copolymer (hereinafter referred to as copolymer A).
The infrared absorption spectrum of the copolymer A is shown in FIG. 2. In FIG. 2, there are observed a stretching vibration of >C.dbd.O (ester group) at 1,730 cm.sup.-1 and a stretching vibration of methylene group at 2,950-2,850 cm.sup.-1.
The .sup.13 C-NMR spectrum of the copolymer A is shown in FIG. 3.
The composition of the copolymer A was calculated from the chemical shift of the .sup.13 C-NMR spectrum. Exceptionally, the vinyl chloroacetate content was determined according to fluorescent X-ray analysis. The results are shown in Table 1.
The viscosity-average molecular weight [M] of the copolymer A was measured as follows. The result obtained is shown in Table 1.
[.eta.]=31.4.times.10.sup.-3 [M].sup.0.68 (ml/g)
[Polymer Handbook IV-10, 1975, J. Brandrup, E. H. Immergut, A Wiley-Interscience Publication]
The copolymer A was kneaded with the crosslinking agent and others shown in Table 2 to obtain a novel acrylic acid ester copolymer composition.
The composition was crosslinked. The properties of the vulcanized rubber were measured according to JIS K 6301. The results obtained are shown in Table 2.
EXAMPLES 4-9 AND COMPARATIVE EXAMPLES 1-3
(Preparation of novel acrylic acid ester copolymer, composition comprising said copolymer, comparative copolymer and comparative composition comprising said comparative copolymer)
A monomer mixture as shown in the polymer composition of Table 1 was subjected to reaction under the same conditions as in Example 3 using the same reactor as in Example 3 to obtain a copolymer (hereinafter referred to as copolymers B-J).
The compositions and molecular weights of the copolymers B-J were determined in the same manner as in Example 3. The amount of allyl glycidyl ether was determined by determining the amount of the epoxy group, and the amounts of vinyl acrylate and dihydrodicylopentadienyloxyethyl acrylate were determined by iodometry.
The compositions of the copolymers B-J are shown in Table 1. The compounding recipes and vulcanized rubbers of the compositions comprising the copolymers B-J are shown in Table 2. The properties of the crosslinked products of said compositions are shown in Table 2 and FIG. 4.
As is clear from these results, the novel acrylic acid ester copolymer compositions of this invention are superior to conventional copolymer compositions in heat resistance, low-temperature resistance and oil resistance.
EXAMPLES 10-12 AND COMPARATIVE EXAMPLES 4-5
(Preparation of novel acrylic acid ester copolymer, composition comprising said copolymer, comparative copolymer and comparative composition comprising said comparative copolymer)
In the same manner as in Example 3, a monomer mixture as shown in the polymer composition of Table 3 was subjected to reaction until a conversion of 80% was reached, to obtain a copolymer (hereinafter referred to as copolymers K-O).
The compositions of the copolymers K-O were determined from the .sup.13 C-NMR spectra in the same manner as in Example 3. The results obtained are shown in Table 3.
The viscosity-average molecular weights [M] of the copolymers K-O were measured as follows, to obtain the results shown in Table 3:
[.eta.]=54.times.10.sup.-3 [M].sup.0.68 (ml/g)
[Polymer Handbook IV-10, 1975, J. Brandrup, E. H. Immergut, A Wiley-Interscience Publication]
To 100 parts of each of the copolymers K-O were added 5 parts of zinc oxide, 1 part of stearic acid, 60 parts of SRF carbon black, 5 parts of dioctyl phthalate, 0.5 part of sulfur, 1.5 parts of tetramethylenethiuram disulfide and 2.0 parts of N-cyclohexyl-2-benzothiazylsulfenamide. They were mixed by a roll. The mixture was crosslinked by a press at 160.degree. C. for 20 minutes to prepare a crosslinked sheet. The properties of the crosslinked product were measured in the same manner as in Example 3. The results are shown in Table 3.
As is clear from Table 3, the novel acrylic acid ester copolymer compositions of this invention are superior to conventional acrylic acid ester copolymer compositions in balance of heat resistance, low-temperature resistance and oil resistance.
EXAMPLES 13-15 AND COMPARATIVE EXAMPLES 6-8
(Preparation of rubber composition comprising novel acrylic acid ester copolymer and comparative rubber composition)
The copolymer H or I shown in Table 1 and various compounding agents shown in Table 4 were kneaded by a roll to obtain a rubber composition. From this rubber composition was prepared a crosslinked sheet. The crosslinked sheet properties were measured in the same manner as in Example 3. The results obtained are shown in Table 4 and FIG. 5. As is clear from Table 4, the rubber compositions comprising the novel acrylic acid ester of this invention as an essential component are superior to conventional rubber compositions in balance of heat resistance, low-temperature resistance and oil resistance.
EXAMPLES 16-17 AND COMPARATIVE EXAMPLES 9-10
(Preparation of rubber composition comprising novel acrylic acid ester and comparative rubber composition)
Using an NBR (as a copolymer) and various compounding agents as shown in Table 5 and employing the same procedure as in Example 13, rubber compositions were prepared. The compositions were crosslinked and the crosslinked products were measured for properties. The results are shown in Table 5.
As is clear from Table 5, the rubber compositions comprising the novel acrylic acid ester of this invention as an essential component are superior to conventional rubber compositions in balance of heat resistance, low-temperature resistance and oil resistance.
EXAMPLES 18-25
(Preparation of novel acrylic acid ester copolymer, composition comprising said copolymer)
A monomer mixture as shown in the polymer composition of Table 6 was subjected to reaction under the same conditions as in Example 3 using the same reactor as in Example 3 to obtain a copolymer (hereinafter referred to as copolymers P-W).
The compositions and molecular weights of the copolymers P-W were determined in the same manner as in Example 3. The amount of allyl glycidyl ether was determined by determining the amount of the epoxy group, and the amounts of vinyl acrylate were determined by iodometry.
The compositions of the copolymers P-W are shown in Table 6. The compounding recipes and vulcanized rubbers of the compositions comprising the copolymers P-W are shown in Table 7. The properties of the crosslinked products of said compositions are shown in Table 7.
As is clear from these results, the novel acrylic acid ester copolymer compositions of this invention are superior in heat resistance, low-temperature resistance, oil resistance and compression set.
Claims
What is claimed is:
1. An ester group-containing (meth)acrylic acid ester (co)polymer composed of (A) 5-100% by weight of an ester group-containing (meth)acrylic acid ester of the general formula (I) ##STR7## wherein R.sup.1 is a hydrogen atom or a methyl group, R.sup.2 is a C.sub.3-20 alkylene group, R.sup.3 is a C.sub.1-20 hydrocarbon group or its derivative, and e is an integer of 1-20 and (B) 0-95% by weight of another monomer copolymerizable with the component (A).
2. The (co)polymer according to claim 1, wherein in the general formula (I), R.sup.1 is a hydrogen atom, R.sup.2 is --C.sub.5 H.sub.10 --, R.sup.3 is --C.sub.2 H.sub.5 or --C.sub.8 H.sub.17, and l is 1-5.
3. An ester group-containing (meth)acrylic acid ester copolymer composed of (A) 5-30% by weight of an ester group-containing (meth)acrylic acid ester of the general formula (I) according to claim 1, (B-1) 50-90% by weight of at least one unit selected from the group consisting of an alkyl acrylate in which the alkyl has 3 to 21 carbon atoms and an alkoxy-substituted alkyl acrylate, (C) 0.1-10% by weight of a crosslinking monomer and (B-2) 0-30% by weight of other monomer copolymerizable with the components (A), (B-1) and (C).
4. An ester group-containing (meth)acrylic acid ester copolymer composed of (A) 5-50% by weight of an ester group-containing (meth)acrylic acid ester of the general formula (I) according to claim 1, (B-3) 10-40% by weight of at least one unit selected from the group consisting of butyl acrylate and 2-methoxyethyl acrylate, (C) 0.1-10% by weight of a crosslinking monomer and (B-4) 0-45% by weight of other monomer copolymerizable with the components (A), (B-3) and (C).
5. An ester group-containing (meth)acrylic acid ester copolymer composed of (A) 5-50% by weight of an ester group-containing (meth)acrylic acid ester of the general formula (I) according to claim 4, (D) 25-60% by weight of a conjugated diene compound, (E) 20-45% by weight of an .alpha.,.beta.-ethylenically unsaturated nitrile compound and (B-5) 0-20% by weight of other monomer copolymerible with the components (A), (D) and (E).
6. A crosslinkable (co)polymer composition comprising an ester group-containing (meth)acrylic acid ester (co)polymer according to claim 1 and a crosslinking agent.
7. A crosslinkable copolymer composition comprising an ester group-containing (meth)acrylic acid ester copolymer according to claim 3 and a crosslinking agent.
8. A crosslinkable copolymer composition comprising an ester group-containing (meth)acrylic acid ester copolymer according to claim 4 and a crosslinking agent.
9. A crosslinkable copolymer composition comprising an ester group-containing (meth)acrylic acid ester copolymer according to claim 5 and a crosslinking agent.
10. A rubber composition comprising 100 parts by weight of a polymer having rubber elasticity, 5-50 parts by weight of an ester group-containing (meth)acrylic acid ester of the general formula (I) according to claim 1 and 0.1-10 parts by weight of a crosslinking agent.
Patent Citations (9)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US2499393 | 1950-03-01 | Kenyon et al. | |
| US2559635 | 1951-07-01 | Kenyon et al. | |
| EPX86401 | 1983-08-01 | ||
| DEX3513356 | 1986-10-01 | ||
| JPX44-20626 | 1969-09-01 | ||
| JPX47-11490 | 1972-04-01 | ||
| JPX61-53242 | 1986-03-01 | ||
| JPX61-134350 | 1986-06-01 | ||
| JPX63-161005 | 1988-07-01 |
Non-Patent Literature (2)
- Journal of the Society of Rubber Industry, Japan, 53 (6) pp. 367-378 (1980).
- Japanese Patent Application Kokai No. 52-98048 with its English Abstract.