KR790001048B1 - Polymerizates of oleting nitriles and diene rubber - Google Patents

Abstract

Graft acrylonitrile-butadiene-indene polymer, having good impact resistance, low permeability to gases, and high softening temp., was prepd. by grafting acrylonitrile and indene on nitrile rubber. Thus, an aq. emulsion of acrylonitrile 70, indene 17.5 and rubber latex 15 parts was polymd. at 60≰C for 6hr using K2S2O8 as catalyst and limonene dimercaptane, and then the reaction mixt. was heated to 70≰C and K2S2O8 0.2, indene 12.5 and limonene dimercaptane 0.5 part were added over a period 5hr to give I.

Description

Process for preparing polymer of olefinic nitrile and diene rubber

The present invention relates to a method for preparing a polymer used as a barrier to penetration of gas or vapor from a conjugated diene monomer, an olefinically unsaturated nitrile and diene due to its high impact resistance, low gas permeability, high softening temperature, and particularly low creep resistance. It is about.

The polymer product of the present invention is prepared by polymerizing a large amount of olefinically unsaturated nidrill, for example acrylonitrile and a small amount of indene, in the presence of a preformed rubbery polymer composed of a conjugated diene monomer such as butadiene.

Conjugated diene monomers useful in the present invention include butadiene-1,3, isoprene-droxoprene-bromoprene, cyanoprene, 2,3-dimethylbutadiene-1,3 and the like. As the most suitable monomer for the purposes of the present invention, butadiene and isoprene are most preferred because of their immediate availability and excellent copolymerizability.

(여기서 R은 수소, 탄소수 1 내지 4의 저급알킬그룹 또는 할로겐이다)의 알파, 베타－올레핀성 불포화 모노 니트릴이며, 이런 화합물에는 아크릴로니트릴, 알파－클로로아크릴로니트릴, 알파－플루오로아크릴로니트릴, 메타아크릴로니트릴, 에타이크릴로니트릴 등이 있다. 이 중에서도 본 발명에 가장 적합한 올레핀성 불포화 니트릴은 아크릴로니트릴이다.Olefinic unsaturated nitriles useful in the present invention have a structural formula

Alpha, beta-olefinically unsaturated mononitrile, wherein R is hydrogen, a lower alkyl group or halogen having 1 to 4 carbon atoms, and such compounds include acrylonitrile, alpha-chloroacrylonitrile, alpha-fluoroacrylo Nitrile, methacrylonitrile, ethacrylonitrile and the like. Among these, the most suitable olefinic unsaturated nitrile for this invention is acrylonitrile.

Indene (1-H-indene), coumarone (2,3-benzofuran) and mixtures thereof are useful as monomers of the present invention, and indene is most preferred. The polymer composition of the present invention can be prepared by a polymerization technique such as bulk polymerization, liquid polymerization and emulsification or suspension polymerization by adding monomers and other components in batches, continuously or intermittently, among which emulsion polymerization is most suitable. Do. The polymerization process is preferably carried out in an aqueous medium in the presence of a polymerization initiator and an emulsifier to produce free groups, substantially removing oxygen molecules at a temperature of 0 ° to 100 ° C.

The rubbery polymer of the present invention is a homopolymer of the conjugated diene monomer as well as a copolymer of these dienes with other monomer components such as acrylonitrile, styrene, ethyl acrylate and mixtures thereof, wherein the conjugated diene monomer Is present at least 50% of the total weight.

(여기서 R은 상술한 바와 같아)을 갖는Preferred polymer compositions of the invention are (A) structural formulas

(Where R is as described above)

50 parts by weight of at least one nitrile and (B) 100 parts by weight of a substance consisting of two of 10 to 50% by weight of at least one compound selected from indenes and coumarones; It is prepared by polymerization in the presence of 1 to 40 parts by weight of a rubbery polymer composed of at least 50% by weight and at least 50% by weight of at least one compound selected from styrene, acrylonitrile and ethyl acrylate.

(여기서 R은 수소, 탄소수 1 내지 4의 저급알킬그룹 또는 할로겐이다)을 갖는 적어도 하나의 니트릴 50 내지 90중량%와 (B) 인덴 및 쿠마론 중에서 선택한 적어도 하나의 화합물 10 내지 50중량%로 구성되는 물질 100중량부를, (C) 부타디엔 및 이소프렌 중에서 선택한 공액디엔 모노머 50중량%이상, 및 스티렌, 아크릴로니트릴 및 에틸 아크릴레이트로 구성되는 그룹 중에서 선택한 적어도 하나의 화합물 50중량% 이하로 구성되는 고무상 중합체 1 내지 40중량부의 존재하에서 중합시킴을 특징으로 한다. 여기서 (A)의 총량 또는 일부분 및 (B)의 일부분은 종합반응이 개시될 때 이미 존재하고 (B) 또는 (A)+(B)의 잔류분은 중합공정 중에 연속적으로 또는 몇 등분으로 나누어 가한다.Preferred processes of the present invention employ (A) structural formula using free groups in an aqueous emulsion at a temperature of 0 to 100 ° C.

Consisting of 50 to 90% by weight of at least one nitrile having hydrogen, a lower alkyl group or halogen having 1 to 4 carbon atoms or halogen and (B) 10 to 50% by weight of at least one compound selected from indene and coumarone 100 parts by weight of the substance comprises (C) at least 50% by weight of a conjugated diene monomer selected from butadiene and isoprene and at least 50% by weight of at least one compound selected from the group consisting of styrene, acrylonitrile and ethyl acrylate. And polymerized in the presence of 1 to 40 parts by weight of the free polymer. Wherein the total amount or part of (A) and part of (B) are already present at the start of the synthesis reaction and the residues of (B) or (A) + (B) are divided continuously or in several parts during the polymerization process. do.

In particular, the present invention polymerizes a mixture of acrylonitrile and indene in the presence of a pre-formed copolymer of butadiene-1,3 and acrylonitrile to provide excellent impact strength, excellent impermeability to gas and vapor, and improved ASTM. The present invention relates to the production of a product having a heat distortion temperature and the like. Preferably the acrylonitrile-inene monomer component should contain 60 to 90 weight percent acrylonitrile and 10 to 40 weight percent indene. In most cases the permissible impact resistance is 0.5 ft · lb or more of Izod impact per inch of notch.

Preferred rubbery copolymers of butadiene-1,3 and acrylonitrile contain at least 50% by weight butadiene based on the total amount of butadiene and acrylonitrile, preferably 50 to 90% by weight, more preferably Should contain 60 to 80% by weight of polymerized butadiene.

In the above polymerization step, it is suitable to use 1 to 40, preferably 1 to 20 parts of rubbery diene polymer per 100 parts of the mixed amount of acrylonitrile and indene. Typically, it has been found that increasing the relative amount of rubbery diene polymer in the final polymer product increases the impact strength but reduces the impermeability to gases and vapors to some extent. In normal cases, it is desirable to use a sufficient amount of rubbery diene polymer to give the polymer product the desired impact strength and to maintain optimal impermeability to gases and vapors.

The polymer composition of the present invention is a thermoplastic that can be thermally deformed into a wide variety of useful products by conventional methods used in the case of known thermoplastic polymer materials, such as extrusion, grinding, molding, stretching, blowing, etc. Easy to process The polymer products of the present invention have good solvent resistance and impact strength, and because of their low permeability to gases or vapors, these materials can be usefully used in the packaging industry, especially for the manufacture of bottles, films and containers containing liquids or solids. .

In the examples described below, the amounts of each component are expressed in parts by weight unless otherwise specified.

Example 1

(A) Resin is manufactured from the following component.

Sex Division

Water 233

Gafac RE -610 ^* 2

Acrylonitrile 70

Inden 30

Limonene Dimercaptan 0.6

Butadiene / Acrylonitrile 15

Rubber Latex (70: 30 ratio based on solid)

Potassium Persulfate 0.28

^* A mixture of R-O (CH ₂ CH ₂ O-) nPO ₃ M ₂ and [R-O- (CH ₂ CH ₂ O-) n] ₂ PO ₂ M, product of GAF Corporation, where n is 1 A number between 40 and R is an alkyl or alkaryl group, preferably a nonylphenyl group, and M is hydrogen, ammonia or an alkali metal.

(1) First step: 70 parts of acrylonitrile, 17.5 parts of indene, 15 parts of rubber latex and 0.1 parts of limonene dimercaptan dissolved in 225 minutes of water, 2 parts of Gafac RE-610 While stirring, the mixture is heated to 60 ° C. under substantially no oxygen molecules. 0.1 part potassium peroxide is added thereto to initiate the polymerization reaction, and the reaction is continued for 6 hours under these conditions.

(2) Second step: The mixture obtained in the first step was heated to 70 ° C, and then the mixed solution of 0.2 parts of potassium peroxide and 8 parts of water was divided into 6 equal parts and added over 5 hours. Negative indene and 0.5 part limonene dimercaptan are added slowly. The resulting latex is agglomerated and dried to obtain a resin in 88% yield as follows.

ASTM-Heat Deflection Temperature (264psi) 101 ℃

Izod impact strength 1.2 ft.lb/notch 1 inch

Brabender Torque at 230 ° C

(B) The same ingredients and amounts as in Example (A) above are used. Ingredients other than potassium persulfate were fed in a batch, stirred under substantially no oxygen in the molecular phase, and heated to 60 ° C. At this time, potassium persulfate was added, followed by polymerization for 16 hours. The resulting latex is agglomerated and the resin is dried to yield the product in 66% yield. The resin has the following properties.

ASTM-Heat Deflection Temperature (264psi) 108 ℃

Izod impact strength 0.11 ft.lb/notch 1 inch

Brabender Torque 800 to 900mgr at 230 ° C

Example 2

The resin is prepared from the following components.

Sex Division

Water 262

Gafac RE -610 2.25

Acrylonitrile 70

Inden 30

Limonendi mercaptan 0.75

Butadiene / Acrylonitrile Rubber Latex 15

(70: 30 ratio based on solids)

Azobis isobutyronitrile 0.45

70 parts of acrylonitrile, 5 parts of indene, 15 parts of rubber, and 0.25 parts of limonene dimercaptan were suspended in 262 parts of water and 2.25 parts of Gafac RE-610 were stirred under nitrogen atmosphere and heated to 70 ° C. Bis isobutyronitrile is added to initiate the polymerization reaction. The remainder of 25 parts of indene and 0.5 parts of limonenedimercaptan is added continuously over 9 hours, during which time an additional amount of azobis isobutyronitrile (0.35 parts) is added over seven times. The total polymerization reaction is to react for 9 hours at 70 ° C. The latex is agglomerated and dried to obtain a resin having the following properties.

ASTM-Heat Deflection Temperature (264psi) 84 ℃

Izod impact strength 1.7 ft.lb/notch 1 inch

Brabender Torque 2,200mgr

Example 3

The resin is prepared from the following components.

Sex Division

Water 232

Gafac RE -610 3

Acrylonitrile 70

Inden 30

Limonene Dimercaptan 0.75

Butadiene / Acrylonitrile Rubber Latex 15

(70: 30 ratio based on solids)

Azobis isobutyronitrile 0.2

Potassium Persulfate 0.175

A solution obtained by suspending 70 parts of acrylonitrile, 6.51 parts of indene, 15 parts of rubber and 0.25 parts of limonene dimercaptan in 232 parts of water was heated with 65 parts of nitrogen under nitrogen pressure while stirring with 2 parts of Gafac RE-610 and then Negative azobis isobutyronitrile is added to initiate the reaction. In this polymerization reaction, a mixture solution of 23.49 parts of indene and 0.5 parts of limonene dimercaptan is added over 8 hours. In the meantime, the reaction mixture was treated with 0.1 parts of azobisisobutyronitrile at 1 hour after the start of the reaction, and 0.175 parts of potassium persulfate was added in equal portions seven times between 2.5 hours and 6 hours. The resulting latex is aggregated and the resin is dried to give a product having the following properties.

ASTM-Heat Deflection Temperature (264psi) 98 ℃

Izod impact strength 1.25 ft.lb/notch 1 inch

Brabender Torque 3,100mgr

Example 4

The resin is prepared from the following components.

Sex Division

Water 233

Gafac RE -610 2

Acrylonitrile 70

Inden 30

Limonene Dimercaptan 0.6

Butadiene / Acrylonitrile Rubber Latex 15

(65:35 ratio based on solids)

Potassium Persulfate 0.3

(1) First step: 70 parts of acrylonitrile, 17.5 parts of indene, 15 parts of rubber (latex form), 0.15 parts of limonene dimercaptan and 2 parts of Gafac RE-610 emulsion are stirred under nitrogen and heated to 60 ° C. do. 0.1 part of potassium persulfate is added to the reaction mixture to start the reaction, and the reaction is continued for 6 hours.

(2) Second step: After heating the reaction mixture in the first step to 70 ° C., a solution of 0.2 parts of potassium persulfate dissolved in 8 parts of water was added in 6 portions over 6 hours to obtain indene and limonene dimercaptan. The residue is added twice. (After 1.4 hours, 8 parts of indene and 0.25 parts of limonene dimercaptan are added and after 4 hours, 4.5 parts of indene and 0.2 parts of limonene dimercaptan are added). After 6 hours at 70 ° C., the resulting latex was agglomerated with hot aqueous Al ₂ (SO ₄ ) ₃ .18H ₂ O and the resin was washed with boiling water to give a dried resin having the following properties (yield 80 %).

ASTM-Heat Deflection Temperature (264psi) 97 ℃

Izod impact strength 1.04 ft.lb/notch 1 inch

Brabender Torque 2,500mgr

Example 5

The resin is prepared from the following components.

Sex Division

Water 265

Gafac RE -610 2.25

Acrylonitrile 70

Inden 30

Limonene Dimercaptan 0.5

Butadiene / Acrylonitrile Rubber Latex 15

(65:35 ratio based on solids)

Potassium Persulfate 0.3

(1) First step: 40 parts of acrylonitrile, 10 parts of indene, 15 parts of latex rubber, 0.05 parts of limonene mercaptan, 186.5 parts of water and 2.25 parts of Gafac RE-610 emulsion are stirred in the presence of nitrogen at 60 캜. Heated to. At this time, 0.05 part of ammonium persulfate was added, and the polymerization was carried out for 6 hours under these conditions.

(2) Second step: The mixture obtained in the first step is diluted with 78.5 parts of water and heated to 70 ° C. A mixture of 30 parts of acrylonitrile, 20 parts of indene and 0.45 parts of limonene dimercaptan is added over 5 hours, with 0.25 parts of ammonium persulfate added in 5 portions in between. The polymerization reaction in this step is carried out at 70 ° C. for a total of 6 hours. The resulting latex is agglomerated with hot alum and washed thoroughly with hot water. The dried resin has the following characteristics.

ASTM-Heat Deflection Temperature (264psi) 101 ℃

Izod impact strength 0.83 ft.lb/notch 1 inch

Brabender Torque 2,800mgr

Example 6

Repeating the process of Example 1 (A) with 75 parts of acrylonitrile and 25 parts of indene yields similar results to the above.

Example 7

Repeating the process of Example 1 (A) using 65 parts acrylonitrile and 35 parts indene yields similar results to the above.

Example 8

Repeating the process of Example 1 (A) using 80 parts of acrylonitrile and 20 parts of indene yields similar results as above.

Example 9

If the process of Example 1 (A) is repeated using 10 parts of butadiene-acrylonitrile rubber (solid basis), the impact resistance of IZOD slightly decreases, but results similar to the above are obtained.

Example 10

If the process of Example 1 (A) is repeated using 20 parts of butadiene-acrylonitrile rubber (solid basis), the Izod impact resistance is further improved, but similar results are obtained.

Claims (1)

(A) structural formula

50 to 90% by weight of at least one nitrile having R, wherein hydrogen is a lower alkyl group or halogen having 1 to 4 carbon atoms (B) 100 parts by weight of a substance consisting of two of 10 to 50% by weight of at least one compound selected from indene and coumarone, (C) 1 to 40 parts by weight of at least 50% by weight of a conjugated diene monomer selected from butadiene and isoprene and up to 50% by weight of a rubbery polymer of at least one compound selected from styrene, acrylonitrile and ethyl acrylate Initiation of free radicals in an aqueous emulsion at a temperature of 0 to 100 ° C., wherein the total amount or part of (A) and part of (B) are already present when the polymerization is initiated and (B) or (A) + ( A polymerization method in which the remainder of B) is added continuously or in an increase during the polymerization reaction.