JPS5849741A - Composition of graft copolymer and resin - Google Patents

Abstract

PURPOSE:A composition of low production costs that is composed of a specific alpha-methylstyrene/nitrile monomer/diene rubber graft copolymer and of a resin containing styrene/acrylonitrile, thus showing high performance in physical properties, especially impact strength. CONSTITUTION:(A) A graft copolymer that contains alpha-methylstyrene and a copolymerizable nitrile monomer grafted onto the major chains of diene rubber wherein the rubber content is 25-75wt% and the diene rubber is polybutadiene or poly (butadiene/styrene), and has a average particle size in rubber major chain particles of 400-1,500Angstrom is combined with (B) a resin containing styrene and acrylonitrile so that the weight ratio of A/B becomes 20/80-45/55, preferably 25/75-35/65. The nitrile monomer in component A is acrylonitrile.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to blends of graft copolymers and resins. 4IlFiC1 This is α-methylstyrene/nitrile monomer/dieneim graft copolymer and styrene/
% with acrylonitrile or with styrene/acrylonitrile/α-methylstyrene resin.

The number average particle size of the particles of the dieneim (to which the α-methylstyrene and the copolymerizable nitrile monomer are grafted) is from 4゛00 to 1500 Å) o-
0 monomer town and M, which is the diameter up to M, are the main trunk (5pine: spine) S
During the grafting reaction, the main parts of Ml and M2 copolymerize to form Ml −, , Ms 'fl
This will result in a resin that is not itself part of the graft copolymer but will not separate from it. 19
Co-pending U.S. Patent Application No. 824 filed August 15, 1977
, 467 (Geelan), and U.S. Pat.
908.661; 3,367,995 and 3.5
No. 94,453 discloses graft copolymers of acrylonitrile and α-methylstyrene and/or styrene which are graft polymerized onto Zoeza rubber, and U.S. Pat. No. 3,594,453 discloses graft copolymers with even smaller particles. Discloses the use of ultra-fine (average particle diameter generally less than 2000 angstroms) rubber. There is no disclosure of the formulation of such a graft polymer and the desired resin in this application and the three patents; however, despite the VC, using the examples cited above, the graft polymer in this application and patent Analysis of the copolymer product was carried out using M1-
Obviously, such resins could not contain monomers not used in the original grafting mixture, respectively. 3.624,
'183 discloses that graft copolymers can be blended with separately prepared resins; the former patent ('936) blends resins of acrylonitrile, α-methylstyrene, and, in some cases, styrene. disclosed graft polymers of nitrile monomers, styrene or α-methylstyrene and polybutadiene, in which the graph) /Is4 fat ratio a50 from 150 to 70/30
The patent does not mention the size of the main particle of the latter patent ('183). Discloses a graft copolymer with polyzotathiene of large particle size (average particle diameter from 2000 to 5000 angstroms) (&)% nitrile monomer (b) α-methylstyrene (AMP), and (e) small particle size ( e
When a graft copolymer of the dieneim of p@) is blended with the separately prepared resins of (S) styrene, (1) acrylonitrile, and optionally (clα-methylstyrene), the resulting formulation is very unexpectedly Even if the separately made resin is originally present in the graft copolymer product (i.e., M, -M, as previously discussed).

The formulations described and claimed herein are generally found to have substantially better physical properties (particularly impact strength) than formulations that are identical to the resin (resin). This is because APE rubber can be produced more cheaply due to its large particle size (lpa).

In the production of the graft polymer of the present invention, the copolymerizable monomer is preferably acrylonitrile (CN); however, methacrylonitrile and methacriminitrile can also be effectively used. Mixtures of the above nitrile monomers The ratio of α-methylstyrene to nitrile heptamine used during the grafting reaction is from 50 to 90/10 (i.e. Me is from 50 to 90% of the monomer mixture). , and most preferably 60/40 to 80
/20 ◇In the graft copolymer, the ratio Fi of total monomer (α-methylstyrene plus nitrile) to rubber backbone is from 75/25 to 25/75, usually 60
740 to 30/70f and preferably 50'1
The 〇♂im stem, which is from 50 to 40/60, can be any diene such as natural ♂mu, polydetadie Z% polyisoprene, or 90% polychloroprene, and can be prepared using techniques known in the art. The preferred diene imes that may be made are polybutadiene,
and butadiene and up to 4(l) of one or more copolymerizable monomers, preferably styrene.Other copolymerizable monomers that may be used in the backbone are α-methylstyrene, Acrylonitrile, methacriminitrile, methacriminitrile, acryl-13ic acid, acrylic esters, vinylpyridine, and the like; most preferred backbones are polybutadiene or polymers containing up to 10% styrene (zotazoene styrene) Oim, which is a -? system, is used as a latex and typically contains less than 40% solids if all sps. If all sps, the latex may contain up to 60% solids. The wax O im used in the graft polymerization has a number average particle size of from 400 to 1500 angstroms, usually from 400 to 12004, and preferably from 400 to 1000 angstroms. The graft polymerization reaction is described in US Pat. 94.45
May be carried out using the methods taught in No. 5, which patent is hereby incorporated by reference, or published in
Co-pending U.S. Patent Application No. 824,467 filed on the 5th (
According to the latter method, the graft polymerization reaction is carried out in an aqueous medium in which the total amount of water in the reaction mixture is reduced to monomers. from 100 to 250 parts and preferably from 150 to 180 parts per 100 parts of the total amount of solids added.
Other materials present in the grafting reaction mixture are also on the same basis, i.e., 100% of the total monomer plus im solids.
It is possible to use more than 250 parts of water (given in parts by weight), but in this case, the size of the equipment will increase without any increase in productivity, so it is questionable from an economic point of view.0 Normally Any anionic emulsifier used in the grafting reaction may be used. In some cases, the emulsifier is used in conjunction with a dispersing agent such as the sodium salt of a combined alkylnaphthalene sulfonic acid. Examples of emulsifiers that may be used include oleic acid. Emulsifiers are usually sodium and potassium salts of acids and stearic acids, sodium salts of sulfate half esters (e.g. sodium lauryl sulfate), and saponified mixtures of fatty acids and/or rosin acids, such as potassium oleate or sodium lauryl sulfate. and preferably sodium lauryl sulfate is used in combination with the above-mentioned dispersants.The amount of emulsifier used is from 1 part to 4 parts and preferably from 1.5 parts to 2.5 parts. O The graft polymerization catalyst (or initiator) used is a -component system and can be any water-soluble free radical polymerization initiator.
For example, hydrogen peroxide, potassium, sodium, or ammonium persulfates, peracetates, or percarbonates are used alone or in combination. Potassium persulfate initiators are preferred. Amount of initiator used. Fi0.1 to 0.
Up to 8 parts and preferably 0.5 to 0.6 parts.

Molecular weight regulators are optionally included in the reaction mixture. Such regulators are added to inhibit subsequent polymerization and control the molecular weight of the polymer by acting as chain terminators, which in turn Most preferably, the modifier is a tertiary C12, C14 and exts mercaptan. This mixture is a mixture in the approximate proportions of 60/20/20. This mixture is known in this art as Up to 0.7 parts.
The reaction temperature is determined in part by the initiator used, but generally ranges from 125° to 200°F (52-96°C).
% and most preferably from 150° to 17'O'P-1
"t" (66° to 77°Ct 't') "t" h
Le@grafting reaction is carried out in one reaction step under an inert atmosphere.
This is usually done under a nitrogen atmosphere.

The pressure in the reaction vessel is sufficient to maintain the reaction mixture in the liquid phase and is generally between 5 and 90 psi.
At g o, the angle is from 15 to 40 pθigt. Higher pressures can be used, but are not economically justified. Reaction time depends on catalyst concentration, source level, reactor type, and reactant addition rate. In general, the reaction time is O for up to 12 hours, and usually for up to 4 to 8 hours, in a closed tank-type reactor, in which the reaction vessel can be pressurized, preferably with stirring means, depending on the shape of the reactor. As will be understood by those skilled in the art, there is no definitive table; for example, a plug-flow reactor with multiple feed points could be used; in general, the grafting reaction The procedure for carrying out the process is as follows: Place the rubber latex in a reactor, prepare an aqueous solution of the soap ingredients (i.e., emulsifier, dispersant, and chelating agent), and add a portion of it to the initiator and the necessary Add to the latex in the reactor along with additional water and heat the mixture to reaction temperature.The monomer and remaining soap solution are then added over a period of 5 hours, usually about 3 hours, and either continuously or batchwise. Following this addition, an additional Vc 3 hours is typically required to ensure complete reaction. At the end of this time, the reactor is cooled and the graft copolymer is recovered by semi-coagulation and drying techniques. The graft copolymer is thus recovered. can be blended with a resin at any time.This procedure can be modified as will be understood by those skilled in the art.The resin used here is styrene-acrylonitrile (EIAN) or alpha-acrylonitrile. Methylstyrene-styrene-acrylonitrile (
The styrene/acrylonitrile ratio in any 08Alli resin (AeAN) is from 60/40 to 9575, usually from 65/35 to 85/15, and preferably from 70150 to 80/20. Muhimu N resins are 1M 8.5 to 50 ts AON from 15 to 75 ts, and styrene from 15 to 75 ts; usually 1M 8.15 to 45% t from 40 to 60 ts 0 AON, or and preferably 50 to 60% AM, 20 to 60% AON, and 15 to 20% styrene. 010,936;3,288,
731 and 3,624.183, which patents are hereby incorporated by reference.

In the formulation of the invention, the graft copolymer/resin ratio is 2
0/80 to 45,155 degrees, preferably 25/75 to 35/651 degrees. Compounding can be done by standard methods such as by mixing the graft and resin latex together and coagulating or by dry compounding the resin and the graft. The following examples are provided to further illustrate the present invention; however, the examples are for illustrative purposes only and are therefore specific. It goes without saying that this is not intended to limit the scope of the request.

EXAMPLES Various formulations of graft copolymers and resins are made and tested to determine their physical properties. The graft copolymers for Experiment A shown in the following table are made as follows (all parts are by weight and based on 100 parts of Dem backbone plus monomer): 06 Orpm stirrer, reflux condenser. , 2 dripping pouts.

2, fitted with a thermometer and heated in a 66°C oil bath.
Use a vertical reactor. 55 parts of 8pB styrene-butadiene (dry pace, 57m solid latex, approx.
A number average particle size of 0 angstroms, a 7/93 styrene/detadiene weight ratio) is placed in the reactor.

1.6 parts of sodium lauryl sulfate in a second container
．． Stir in 7 parts of distilled water. ◎ Pour 20 parts of potassium persulfate catalyst (0,375 parts) into a third container and stir.
0°C or below) Dissolve in distilled water ◎ Sodium sulfate (0.7
), ethylenediaminetetraacetic acid trisodium salt (0,0
1 part) and naphthalene sulfonate (1.6 parts) are dissolved in 80.7 parts of warm (below 50° C.) distilled water in a fourth vessel.

A portion of the sodium lauryl sulfate solution (2.68 parts) is stirred into a fourth vessel and the resulting solution is added to the reaction vessel. Add the remaining 9.62 parts of sodium lauryl sulfate solution to one of the droplets; 031.1 parts of AMP;
13.9 parts of AON and 0.6 parts MTM are mixed together in a fifth vessel. A portion of this mixture (9.12 parts) is added to the reactor when the reactor temperature reaches 61°C. put in·
Add the remaining 36.48 parts of the AMS-AON-MTM mixture into the other dropper.

When the temperature of the reaction vessel reaches 62° C., begin continuous feeding of monomer and soap solution in the two drops. Addition is completed in 2 hours. Then, heat for 6 hours.
Then cool.

Next, in a separate compounding vessel, a graft copolymer latex of 84.211 (31,91 solids) and a separately prepared 200.9 y of SAM resin emulsion (75 styrene, intrinsic viscosity 0.43. 36.4% solids) and stirred to form a graft-resin formulation. 4.
5F 2596 Solid Antioxidant Emulsion (0,90
part of tri(mixed mono-dinonyl)phenyl phosphite, 0.
45 parts of 2,2'-methylenebis-(4-methyl-6
- Tunylphenol), Oyohi 0.90m [) Alkylated Zophenylamine] are placed in a mixing container and stirred.
Next, add this mixture to 7P Mg5 in 7001 distilled water.
Pour into the coagulation vessel containing the solution at 210°F and stir.Adjust the rate of addition of the mixture to bring the temperature to *2.
After the O addition is complete, the contents of the container are further heated to within 10 °C.
Stir for a minute and collect the solidified material from the mixture by vacuum filtration, then add it to freshly distilled water at 700F. This wash mixture is then heated to 100F' and stir for 10 minutes, then refilter. and a second water wash at room temperature.The recovered graft-resin formulation is dried in an air oven at 60°C for 24 hours.To prepare the formulation for physical property testing, the dried formulation is Add 3.0 parts of ethylene bis(stearamide P) lubricant and mix vigorously to the test material. ．． 2
Machine kneaded for 10 minutes at 0'F and then cut into samples, each at 350F for 3000p.
The physical properties of samples compression molded for 10 minutes under Si are measured according to the following M8TM methods: Notched Izot impact strength, D-256 (Method A); Rockwell hardness,
D-785; Tensile strength; D-638; Heating bending temperature;
D-648° Other formulations in Table 1 are similarly prepared and tested using the ingredients indicated under Table 1 and JJte.
R graft copolymer and! O containing 3A11 resin
This formulation has good impact strength and low viscosity and is suitable for injection molding.Formulation B is where the resin of B is Me/ON.

A is the same as O, except that it is the same resin that is produced during the grafting reaction when the graft used in B is made (the resin emulsion used is 69tIb styrene, contains 44.4% solids, and Intrinsic viscosity number 0.5
6) B has a lower impact strength and a substantially higher viscosity than B, making B less desirable for injection molding. This is new and unexpected. The impact strength of Formulation C, which is similar to A only in the substitution of styrene for Me in the graft copolymer, is extremely poor in impact strength. This makes it unsuitable for applications requiring good impact strength.The formulation uses 1pa = 1'mm (number average particle size of approximately 2100 angstroms) instead of spadem in the backbone of the graft copolymer. The O formulation differs only in that it has a significantly lower impact strength than the O ops! lp compared to mu
The production cost of the compound is higher due to the high price of the compound ◎ The compound differs essentially from the 034. ``Also exhibiting low impact strength, the formulation IF has a low-im grafting (monomer/im ratio of 65/3).
Differences from A in the use of high graft/resin ratio (41,1758,9K vs. 26.8/73.2 in A) , other properties are excellent.

Formulation G uses a very low monomer/rubber ratio in the graft (25/75 vs. 45155 for MU) and a low Graph V resin ratio (20.1/79.9 K vs. 26.8/73.2 for MU). ) The properties are not the best except for the flow properties, which differ from A in the point of use. Compound ■ is the same as G except that 5M87MON resin is used instead of BAN. is within the scope of the present invention, but AsmuN resin (
53% AM8, 18% styrene, 29. Same as A except for the use of %AON). The compound exhibits significant impact strength combined with good tensile strength. This compound once again illustrates the surprising advantages of the present invention. Formulation J has the advantage that the + of AM8 in its graft is replaced by styrene. This substitution substantially reduces impact strength but has little effect on other physical properties.

Compound A OD
11 Graft formulation (parts by weight) Water 200 20
0 200 200 1801ps13B
R manager 55
55epsEiBR Manager 55 55
55 styrene 3
1.1 31.0AM8
31.1 31.1 - 31.1
-AON 13.9 13.9
13.9 13.9 14.0MTM
O, 60, 60, 60, 6-x2s□0
80.375 0.375 0.375 0.375
Conversion rate at 0.305 hours 91 91
99 Compound formulation (parts by weight) Resin mold 8AN AME! /AON
8mm N SAN SAW resin
73.2 73.2 72. CI 73
,2 72.0g2ft 26,8 2
6,8 28.0 26.8 28.0 Im level 15.4 15.4 15.4
15.4 15.4 Physical properties Hardness (R) 110 109 10
8 117 114 1/8 inch notched%73
ff.

Feet? R/inch 3.0
2.7 0.94 0.67 1.2
Heat Deflection Temperature, 'F (annealed for 4 hours at 185°F+) 210 22
5 210 220 210 tensile strength-
pat 5080 6630 5360
5410 5930350°P uniform viscosity
33 93 27 40 244
00'P muuni viscosity 12 52
10 10 6 * Mouth annealed at 185°F for 2 hours FG ) I
Engineering J200 200
200 200 20055 75
75 55 55-8.1 44.8 17.2 17.2 31.1
23.920.2 7.8 7.8
13.9 13.00.6 0.6 0
．． 6 0.6 0.60°375 0°375
0.375 0.375 0.67590
92 92 91 808AN
BAN AME! /AON ASAN
ASANri8.9 79.9 79.9
7'1.2 74.541.1 20.1 2
0.1 26.8 25. ri15.4 15,
4 15, 4 15.4 lb, 411
4 105 110 110 109
1.2 1.4 3.4 5.5 3
．． 5211 209 223 211*
2226160 4260 4940
5870 605041 27
77 78 7215 9
While particular embodiments of the invention have been shown and described herein, it will be obvious to those skilled in the art that variations and modifications may be made without departing from the essence of the invention; The scope of the claims extends to all changes and modifications that fall within the true axis and concave nature of the present invention.

Claims (1)

[Scope of Claims] (1) (A) Grafted onto the main stem of Dienvime
A blend comprising a graft copolymer comprising methylsunarene and a copolymerizable nitrile monomer, and (B) a resin comprising styrene and acrylonitrile, wherein the weight ratio of graft copolymer to resin is from 20/80 to 45155; The im content of the copolymer is 25 to 75 mm, and the number average particle size of the male backbone particles is 400 to 1500 mm in diameter. (2) Formulation # according to claim (1), wherein the copolymerizable nitrile monomer is 7-crylonitrile.
#0 (3) Claim item (1) Kff in which the number average particle size is from 400 to 1000 mm in diameter
(4) A formulation 0 according to claim (1), wherein the im content of the graft copolymer i- is from 40 to 70% by weight; (5) The weight ratio of graft coprimer to resin is 25/75
(6) Blend 0 according to claim 4, wherein the copolymerizable nitrile monomer is 7-cryloetrile. (71-?A The number average particle size of the main particle is 400 mm in diameter.
A formulation according to claim 4, wherein the formulation has a molecular weight of from 1000 Å to 1000 Å. (8) The graft copolyi contains rD1 α-methylstyrene, about 55% poly(butadiene/styrene), and about 14% acrylonitrile; about 75% resin
of styrene and about 25% acrylonitrile;
And the graph "tocopolymer/resin weight ratio is about 277"
75, wherein the resin is styrene, acrylonidonyl, and α-
The formulation according to claim (1) containing methylstyrene (II) The formulation according to claim (9) in which the copolymerizable nitrile monomer is acrylonitrile. A formulation according to claim 9, in which the number average particle size of the particles is up to 400 to 1000 angstroms in diameter. Compound 〇αj according to claim (9) The weight ratio of graft copolymer to resin is 25/75
35/65 to 35/65 O a4 A formulation according to claim A O in which the copolymerizable nitrile monomer is acvcI et tolyl O O A formulation according to claim 1, wherein the number average particle size of the particles of the injection matrix is from 400 to 1000 angstroms in diameter. of poly(butadiene/styrene) and about 14% acrylonitrile; about 53% resin
of α-methylstyrene, about 29% of acrylonitrile,
and about 18% styrene; and the graft copolymer/resin weight ratio is about 27773.