JPS63245458A - Blend consisting of epdm graft terpolymer and acrylate rubber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION 3. [Detailed Description of the Invention] The present invention relates to rubber reinforced resins such as improved f'Lfc rubber reinforced styrene acrylonitrile resins. More particularly, the present invention relates to rubber reinforced resins having an improved combination of weather resistance and physical properties.

British patent application GB2142034A (1985, 1, 9
In particular, (A) aromatic and nyl monomers 10 to 90
%, a continuous phase consisting of 10-40% α,β-unsaturated nitrile monomer and 0-80% methyl methacrylate;
Alkyl acrylates with 12 carbon atoms 70-98
%, copolymerizable vinyl monomer 1.92-27% and polyfunctional vinyl monomer 0.08-3%, particle size 0.
Graft copolymer consisting of dispersed particles of 1-0.45μ poisonous acrylate rubber; (B) aromatic and nil monomer 1
0-90%, α, β-unsaturated nitrile monomer 10-4
and (C) an aromatic vinyl monomer 1
0-90%, α, β-unsaturated nitrile monomer 10-4
0% and methyl methacrylate and 0 to 80% of methyl methacrylate, with a total rubber particle content of 5 to 40%. This document also describes that these three-component compositions contain certain other three-component compositions in which the acrylate rubber component is a homopolymer of butyl acrylate rather than a copolymer of butyl acrylate and acrylonitrile or a copolymer of butyl acrylate and styrene or a copolymer of butyl acrylate and methyl methacrylate. It is taught to provide a product that is superior to the component composition. For example, the British gazette's Clothes 1 Diagnosis.

In contrast to such prior art, the present inventors have developed a novel 31'y-containing acrylate based on a grafted and crosslinked alkyl acrylate homopolymer, which is better than any of the examples and comparative examples of the above-mentioned English-Japanese gazette. The present invention provides a rubber-reinforced thermoplastic polyblend consisting of an elastomer comprising both an EPDM terpolymer rubber and an acrylate rubber and a matrix polymer. . The weatherability of both the EPDM and the acrylate rubber in the compatibilized blend of the present invention provides the composition with superior weatherability and an improved combination of gloss, toughness and ductility compared to known weatherable rubber reinforced resins. has. More particularly, the present invention is a rubber-reinforced thermoplastic polyblend comprising a matrix polymer and a mixture of at least two elastomers dispersed in an amount ranging from 2 to 40 weight percent:
The IJ sox slimer is comprised of both styrene and acrylonitrile; at least the first elastomer is a styrene-acrylonitrile-grafted EPDM terpolymer rubber; the second elastomer is a grafted and crosslinked homopolymer of a C0-a alkyl acrylate rubber; The grafted material is a polyblend containing styrene acrylonitrile, and the M ratio of grafted EPDM rubber to grafted acrylate rubber is in the range of 10:90 to 9:210.

The preferred bond of the elastomer in the polyblend is 5-35
% heavy crying.

EPD for producing grafted elastomer used in the present invention
M rubber is well known in the art. Their disclosures and manufacturing methods are disclosed in U.S. Patent Nos. 3,489,821 and 4,202,948.
These teachings are incorporated herein by reference. E: Although various α-monoolefins are used in the production of PDM rubber, these elastomers are basically terpolymers of ethylene, propylene, and ethylenically unsaturated copolymerizable nonconjugated diene monomers. Non-limiting examples of suitable dienes include synchropentadiene, methylidene norbornene, ethylidene norbornene and
, 4-hexadiene.

Methods for making EPDM kraft copolymers are also well known in the art. For example, EPDM/methyl methacrylate kraft copolymers are disclosed in U.S. Pat.
, 489.822 and 3,642,950 by grafting methyl methacrylate onto an EPDM backbone polymer.

The acrylate rubbers used for grafting in the present invention are also well known in the art, such as US+IP! F3,830
, No. 878, No. 4.341,883, No. 3,944,
No. 631, 3. fi 91,260 and fi 4,22
No. 4.419. Preferred acrylate rubbers are crosslinked homopolymers of CI-a alkyl acrylates, especially butyl acrylate or 2-etherhexyl acrylate. Preferred acrylate rubbers consist of polybutyl acrylate and a crosslinker, such as various di- and trivinyl substituted crosslinkers, in an amount of up to about 5% by total rubber weight.

Preferably, the crosslinked acrylate rubber is made by an emulsion process. When using emulsion-polymerized acrylate rubber, it is known that it is partially agglomerated in order to widen the particle size distribution of the resulting acrylate rubber and improve the resin's strength and resistance to corrosion. It is preferable.

Furthermore, rubber particles can be grown to various sizes using conventional inoculation techniques, and a mixture of large particles and small particles thus prepared can be used to produce grafted rubber. The volume average particle size of acrylate rubber is 500
~10.00 OA. This rubber is 3. OU U~
Large particles with a volume average particle size of 10,000 mm and 500 mm
It has small particles with a volume average particle diameter of ~2,500λ.

In a preferred embodiment, the acrylic rubber has a molecular weight of 500 to 2,40
It has a volume average particle size of 0. The volume average particle diameter is US%fFF4,4 in the form of rubber latex before grafting.
It can be measured by transmission electron microscopy or dynamic chromatography as described in No. 19.496.

Grafting of acrylate rubbers is also well known to those skilled in the art, such as U.S. Pat.
No. 1,883, No. 3,944.633, No. 3,691
．． No. 260 and No. 4.224.419. The crosslinked acrylate rubber is preferably grafted by an emulsion method. Graphs for both EPDM and acrylate rubber) t changes over a wide range. The grafting percentage (weight of attached rigid phase/weight of rubber x 1oo) is from about 5 to about 150. The preferred graft ratio is 10 to 10
It is in the range of 0. The desired grafting rate depends on the particle size.

Larger rubber particles generally have less graft a. Grafting monomers suitable for use in the grafting reaction include the gpvy described above and any suitable polymerizable monomer that forms a graft bond to the acrylate rubber substrate.

Monomer mixtures, ie copolymerizable monomers, may also be used. Although each rubber substrate is preferably grafted with the same matrix grafting polymer or copolymer, different grafting matrices can be used if compatible. Methyl methacrylate and styrene/acrylonitrile (S
AW) is an example of a compatible grafting polymer.

By appropriately selecting the amount and particle size of grafted EPDH, the amount of crosslinking, and the total amount of acrylate rubber used in the final blend, a wide range of product properties can be created.

In addition to the grafted acrylate rubbers and EPDM-f rubbers described above, the compositions may optionally contain other saturated rubbery components, such as vinyl acetate rubber, hydrogenated diene rubbers (hydrogenated polybutadiene, blocks of butadiene and monovinylidene aromatic monomers). hydrides of copolymers, etc.), course butter polymers of ethylene and other α-olefins (ethylene propylene rubber, etc.), and chlorinated polyethylene. Preferred elastomers consist essentially of EPDM rubber and acrylate rubber.

The matrix consists solely of the grafted matrix polymer and non-grafted tomatolink polymer created during the grafting process, although other compatible matrix polymers may also be added separately. The separately added MUL-+J LUX may be the same as or different from the above-mentioned grafted hard phase.

Preferred examples of grafted or non-grafted matrix or hard phase polymers include polymers of alkyl methacrylates and their interpolymers with one or more different copolymerizable ethylenically unsaturated polar comonomers, polymers of vinyl chloride and their interpolymers with one or more different copolymerizable ethylenically unsaturated polar comonomers. Interpolymers with the above copolymerizable ethylenically unsaturated polar comonomers are included.

Examples of preferred polar comonomers in the matrix include alkyl acrylates, tolyl methacrylates, vinyl acetate, alkyl methacrylates, and the like. Preferred matrix polymers consist of styrene acrylonitrile copolymers or homopolymers or interpolymers of methyl methacrylate. The most preferred matrix resin has a styrene/acrylonitrile weight ratio of about 60:40 to 95.
:5 styrene/acrylonitrile.

The grafted EPDM and acrylate rubber are mixed in the presence or absence of additional matrix polymers by any suitable means. In a preferred embodiment, the two resins are simply combined and melted under vigorous stirring. A mixer, a mill, an extruder, or other appropriate equipment may be used to produce the blend.

Additional additives may also be present in the resulting polyblend to modify the properties of the resin. Examples include pigments, fillers,
These include processing aids, antioxidants, stabilizers, and UV stabilizers.

The blend of the present invention can be used in applications for which AES resins have traditionally been used effectively. For example, it can be kneaded with additional resins such as polycarbonate, polysulfone, nylon, borifuenic ether, etc. to form coextruded laminates or molded articles of complex shapes.

The present invention will be briefly explained with reference to Examples, but these are merely illustrative and do not limit the scope of the invention. Circumference % indicates heavy electric %.

Production of butyl acrylate rubber/'/ atstOH1,5Of, Na HCOs
3. OU t, acetic acid 1.711117° dodecylbenzenesulfonic acid sodalite M3. or 32% active polystyrene seed latex (approximately 3 ooi) st4r and water 1389F into the reactor. Awakening? - and heat to 65° C. with stirring at 175 RPM. Over a period of 3 hours, take 8 mouthfuls of 101 exo-butyl acrylate/trimethyl bromine triacrylate (99.0/1.0). At the same time, at 5 o'clock, an aqueous fluid containing 1.43% sodium dodecylbenzenesulfonate 84
8? Add. After 1.5 hours of monomer addition Ectobutyl acrylate/allyl methacrylate (96/4) 20
t) Add S' at once, then add H,0100r. The latex is heated at 65° C. for 2 hours after addition of the aqueous fluid.

The monomer conversion rate is over 98% and the final particle size is 10
It is 33λ. The gelatin content is 87.5% and the swelling index (measured in methyl ethyl ketone solvent) is 11.4.

A variety of butyl acrylate rubber resins are made by varying the amount of crosslinking, seed size, co-addition time, and other variables known in the art.

SAW grafting of butyl acrylate rubber 117'H' of the butyl acrylate rubber latex prepared above and 100 fe of water were placed in a reactor. Birch acid X from the latex and heat to 85° C. with stirring. Monomer mixture 756 of styrene/acrylonitrile (75/25) containing 0.10 parts of 5-octyl mercaptan over 7 hours
Add f. At the same time, 143% sodium dodecylbenzenesulfonate soap and 0.21% sodium peroxydisulfate
Add the aqueous fluid containing H over a period of 7 hours. After the co-addition is complete, the latex is heated at 85 DEG C. for 0.5 hour to strip off the remaining monomer 1 and stabilized with an anti-acid inhibitor. The conversion is 98% and the final dry resin contains 35.1% rubber. The grafting rate of this resin (adhered rigid phase weight/rubber weight x 100) was 16%, and the non-adhered SAM+
) The molecular weight Mw of the Gid phase is 113.000.

EXAMPLE 1 - Various blends containing 9° styrene acrylonitrile resin and grafted rubber are made. In Comparative Example 9, the rubber was EP
Dkf.

A terpolymer of ethylene, propylene, and 5-ethylidene-2-norbornene grafted with SAN according to the disclosure of Example 1 of U.S. Pat. No. 4,202.948, Af, -180
,000 and kneaded with SAN of S/AN 70/30 to make the rubber resin 23%. The resins of Comparative Examples 7 and 8 were the grafted EPDM rubber resin of Example 9 fS/AN 72/
28 with varying amounts of a styrene acrylonitrile matrix having a Mw of -85,000. The resins of Examples 1-6 are illustrative of the invention and additionally contain the grafted acrylate rubber prepared above. This resin was prepared by combining the resin of Example 9 with an acrylate graft copolymer and an AFW-) 35,000 S/AN 72/28 styrene/acrylonitrile matrix in a full Welding Engineers 2@screw extruder (diameter 0.8 inch/
h) Knead with the former and add 1.2 oz.
Molded circular pieces and test bars (0.5" x 0.125" x 6.5") with a diameter of 2" and a thickness of 2" thick were molded at 425/450 degrees Fahrenheit on a Bossi molding machine at 425/450°F.
shall be. We tested Motosawa and Dart's impact on circular pieces. The test bars were tested for tensile strength, elongation, and isot impact. Melt flow rate (MFR) is AS
TM f) - 230℃, 3800 according to -1238?
It was measured with Further information and results are shown in Table I.

3 4.5 25 30
6771o11.5 0 11.
5 10810 ] 8 0 18
149”23 0 23 17 fuck
I Ty Tr Izot MFR Gloss Impact 6597 5376 1.4
4.1 91 320+5685
4718 1.3 1.2
83 320+4743 4313 1.
9 1.7 87 320+49
56 4106 0.7 1.7
320+5354 4544
2.4 3.7 85 320±554
8 4632 11.9 1.3 8
4 320+7917 6584 0.9
7.9 88 320+f'+5
60 5288 4.9 3.2
82 320+5448 4565
12.9 1.0 39 320
+゛ (Notes on different ■) Elongation: ASTM D-638, 0.2 inch/molecule y2 (tanstra yield): Tensile yield,
ASTM D-638, 0.2 inches/minute (lba/
inch) Tr3 (tanstra rupture):
Tensile failure, ASTM D-638, 0.2 in/min (t
bm/ind) Izod': Izod impact, AST
M D-256, 7-notch foot bond inch gloss 5 darkener gloss, measured at 60°C, %, ASTM
D-523 Impact 6: Gardner dart impact, 2 inches x 0.125
Measurement 7 on inch (50 x 3n) piece (inch-bond): Volume average particle size 1033A, graft BAN: Mw1
13.000, S/AN=75/25, graft rate 16
% 8: Volume average particle diameter 740, graft SAN; Mw11
3000, S/AN=90/1092 volume average particle size 1
500 knots, graft SAM: Mw107, OU O1S
/AN=75/2510: Comparative Example Comparing the properties of the resin of the present invention (Examples 1-6) and the resin of Example 7-9, the properties of the resin of the present invention (Examples 1-6) and 7-9 show that the spreadability and gloss measured by elongation are significantly higher. There is also little deterioration in other properties, especially toughness as measured by isot impact and dart impact.

EXAMPLES 10-13 The following examples illustrate the use of acrylate rubber resins and graft and free matrix polymers of various particle sizes. The composition of each resin is as follows.

Example 10°75/25 S/AN grafted 1500.4 monodispersed butyl acrylate rubber resin 33.3%, Example 9
(DEPDMtfFl fat 43.5% and polymethyl methacrylate 23.5% sold by Rohm & Ha-αa Co. under the trade name V920.
2%.

Example 11° 39.1% EPDM resin of Example 9, 20.3% agglomerated phthyl acrylate rubber grafted with SAN (binomial emulsion rubber), SAN (Mw=85,000, S/A
N=72/38) 40.6%.

Example 12゜EPDM of Example 9 34.8%, butyl acrylate rubber grafted with methyl methacrylate (Rohm & Haas KM330') 25.0% and SAN (Mw=
85,000, S/AN 72/28) 40.2%
.

Example 13゜EPDM43.4% of Example 9, 15 grafted with SAN
00A butyl acrylate rubber 16.7%, SAN grafted 5soo, j butyl acrylate rubber 1
3.3% and BAN (Mso=85,000, S/AN
72/28) 26.6%.

These resins were compounded, molded, and tested as in the examples in Table I. The results are shown in Table 1.

Tr Izot Gloss MFR Impact 87 4498 5.0 80
2.9 320+82 5169 1.8
75 3.5 320+29 44
17 2.0 84 2.6 3
20+69 4540 6.0 83
2.3 320+25 4548 3
．． 8 82 2.7 320+ (Note to table ■) Elongation': ASTM D-638, 0.2 inches/molecule ν2: Tensile yield, ASTM D-638, 0.2 inches/min (lba/inch2) Tr3: Tensile failure, ASTM D-638,0,
2 inches/minute (lba/inch2) Izot, Izot Impact, ASTM D-25
6. Feet Bond/Notsuchi inch gloss 5 Ni Gardner gloss, measured at 60°C, %, ASTM
Impact 6: Gardner Dart Impact, 2 inches x 0.125
inch (50mm x 3in) piece (inch-pound)
Measurement 7: Contains 23.2% polymethyl methacrylate y920 manufactured by Rohm and Haas 8: Volume average particle diameter 15ooA; Graft SAM Mw
=231.000% S/N 75/25. 1 acrylate rubber before grafting with a grafting rate of 24% 9:5AN75/25, Mw 193,000, and a grafting rate of 33%.
It aggregated from 50OA to a mixture of 800OA/1500A.

10 Ni'f acrylate rubber grafted with Rohm and Haas methyl methacrylate KM330. The 11 Ni acrylate rubber is a 50/50 mixture of 5500A/1500A particles grafted separately with S/AN 75/25.

The second acrylate rubber was grafted with S/AN 75/25 and had a volume average particle size of 5500A.

The ductility measured by the refractive resistance of the skew-molded rod is determined by the resin test rods described above (0.5 inch x 125 inch x
6.5 inches) by repeated manual bending. The test bar is first bent at an angle of 18° and then immediately bent in the opposite direction at an angle of 360°. Repeat this operation until the rod breaks but cracks. Manual bending life is expressed as the number of bends required (including the initial 180° bend). The average values of the five samples are shown in Table ■.

Table ■ 9° 3.1 8° 2.3 7” 0.4 14.5 26.0 34.4 45.6 54.4 65.6 10 5.4 11 4.4 12 6.8 13 7. 4 14 5.8 Bone Amendment of procedures other than the present invention March 1, 1988 Commissioner of the Patent Office Black 1) Akio Yu 1, Indication of the case 1988 Patent Application No. 76529 2, Title of the invention
, -・-3, Relationship with the case of the person making the amendment Patent applicant name: The Dow Chemical Company 4, agent 5? Contents of 6 amendments to the handwritten specification attached to the I9 correct subject application September 4, 1985 Director General of the Patent Office Kunio Ogawa Hit 1, Indication of the case 1988 Patent Application No. 76529 2 Invention Name of Blend Comprising EPDM Grafted Terpolymer and Acrylate Rubber 3 Relationship with the Amendment Case Name of Patent Applicant The Dow Chemical Company 4 Number of Inventions Increased by Agent 5 Amendment None Contents of 7 Amendment (1) Patent The scope of claims is amended as shown in the attached sheet.

(2) "English-Japanese" on page 6, line 4 of the specification is amended to read "UK."

(3) In line 4 of page 10 of the specification, "has" is corrected to "preferably has a bi+modal distribution."

Claim 1: Matrix polymer and 2 to 4 dispersed therein.
A rubber reinforced thermoplastic polyblend with a mixture of at least two elastomers in an amount ranging from 0% by weight; the matrix polymer consists of both styrene and acrylonitrile; and at least the first elastomer is styrene acrylonitrile grafted EPDM. terpolymer rubber; and the second elastomer is a graft crosslinked homopolymer of alkyl acrylate rubber of C, the graft material includes styrene acrylonitrile, and the weight ratio of grafted EPDM rubber to grafted acrylate rubber is 10: 90-90: Rubber-reinforced thermoplastic polyblend characterized in that it is within the range of 10.

2. The rubber reinforced thermoplastic polyblend of claim 1, wherein the styrene acrylonitrile matrix polymer has a styrene/acrylonitrile ratio of 60:40 to 95:5.

3. The amount of graft polymer in the elastomer component is
The rubber-reinforced thermoplastic polyblend of claim 1, wherein the rubber reinforced thermoplastic polyblend is from about 5 to about 150 weight percent, based on the weight of the rubber.

4. The rubber according to claim 1, wherein the grafted EPDM terpolymer is a graft terpolymer of ethylene, propylene, and a diene selected from the group consisting of synchropentadiene, methylidenenorbornene, ethylidenenorbornene, and 1,4-hexadiene. Reinforced thermoplastic polyblend.

5. A rubber-reinforced thermoplastic polyblend according to claim 1, wherein the grafted acrylate rubber comprises a grafted polymer of butyl acrylate.

6. A rubber-reinforced thermoplastic polyblend according to claim 1, wherein the grafted acrylate rubber is an emulsion polymerized polymer.

7 The volume average particle size of the grafted acrylate rubber is approximately 50
7. The rubber reinforced thermoplastic polyblend of claim 6 having a molecular weight of 0 to about 10,000.

8. The rubber-reinforced thermoplastic polyblend according to claim 7, wherein the grafted acrylate rubber has a bimodal distribution of particle sizes made by agglomeration of small particles or a mixture of separately prepared large particles and small particles.

9 The matrix polymer further contains methyl methacrylate-1
A rubber-reinforced thermoplastic polyblend according to claim 1 containing a homopolymer or interpolymer of .

10. The rubber-reinforced thermoplastic polyblend of claim 5, wherein the acrylate rubber comprises a crosslinked butyl acrylate homopolymer.

Claims (1)

[Claims] 1. Matrix polymer and 2 to 4 dispersed therein.
A rubber reinforced thermoplastic polyblend with a mixture of at least two elastomers in an amount ranging from 0% by weight; the matrix polymer consists of both styrene and acrylonitrile; and at least the first elastomer is styrene acrylonitrile grafted EPDM. terpolymer rubber; and the second elastomer is a graft crosslinked homopolymer of C_1_-_8 alkyl acrylate rubber, the graft material includes styrene acrylonitrile, and the weight ratio of grafted EPDM rubber to grafted acrylate rubber is 10:90-90:
Rubber-reinforced thermoplastic polyblend characterized in that it is within the range of 10. 2. The rubber reinforced thermoplastic polyblend of claim 1, wherein the styrene acrylonitrile matrix polymer has a styrene/acrylonitrile ratio of 60:40 to 95:5. 3. The rubber reinforced thermoplastic polyblend of claim 1, wherein the amount of graft polymer in the elastomer component is from about 5 to about 150 weight percent, based on the weight of the rubber. 4. The rubber according to claim 1, wherein the grafted EPDM terpolymer is a graft terpolymer of ethylene, propylene, and a diene selected from the group consisting of synchropentadiene, methylidenenorbornene, ethylidenenorbornene, and 1,4-hexadiene. Reinforced thermoplastic polyblend. 5. The rubber reinforced thermoplastic polyblend according to claim 1, wherein the graft acrylate rubber comprises a graft polymer of butyl acrylate. 6. The rubber-reinforced thermoplastic polyblend according to claim 1, wherein the graft acrylate rubber is an emulsion polymerized polymer. 7. The volume average particle size of the graft acrylate rubber is approximately 50
7. The rubber reinforced thermoplastic polyblend of claim 6, wherein the rubber reinforced thermoplastic polyblend has a diameter of from 0 to about 1000 Å. 8. The rubber-reinforced thermoplastic polyblend according to claim 7, wherein the graft acrylate rubber has a bimodal particle size distribution created by agglomeration of small particles or a mixture of separately produced large particles and small particles. 9. A rubber-reinforced thermoplastic polyblend according to claim 1, wherein the matrix polymer further contains a homopolymer or interpolymer of methyl methacrylate. 10. The rubber-reinforced thermoplastic polyblend of claim 5, wherein the acrylate rubber comprises a crosslinked butyl acrylate homopolymer.