CN1073577C - Process for preparing acrylonitrile, phenylethylene and polyacrylate graft copolymer - Google Patents
Process for preparing acrylonitrile, phenylethylene and polyacrylate graft copolymer Download PDFInfo
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- CN1073577C CN1073577C CN98121931A CN98121931A CN1073577C CN 1073577 C CN1073577 C CN 1073577C CN 98121931 A CN98121931 A CN 98121931A CN 98121931 A CN98121931 A CN 98121931A CN 1073577 C CN1073577 C CN 1073577C
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- superoxide
- peroxide
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- temperature
- aas resin
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Abstract
The present invention relates to a method for preparing AAS resin, which comprises: firstly, acrylate monomers and peroxide with double bond are copolymerized to obtain polyacrylic ester elastomers with peroxy side groups; then, styrene and acrylonitrile are grafted and copolymerized. The addition of the peroxide is changed, which can regulate the grafting density of the polyacrylic ester elastomers. The addition of grafted monomers is changed, which can regulate the total grafting ratio, and thus, controllable graft polymerization is realized. The grafting ratio of the AAS resin obtained by the method can reach 15% to 40%, and the notch impact strength of a cantilever beam can reach more than 200 J/m.
Description
The invention belongs to chemical technology field, is a kind of preparation method of may command graft polymerization AAS resin.
The technology of preparing of AAS resin (being the graft copolymer of vinyl cyanide, vinylbenzene and polyacrylic ester) is to grow up on the basis of ABS resin.It is with polyacrylic ester as elastomerics, replace the polybutadiene elastomer in the ABS resin, through making with vinylbenzene, GRAFT COPOLYMERIZATION OF ACRYLONITRILE.Because do not contain two keys in the polyacrylate elastomer, the weathering resistance of AAS resin is much more superior than ABS resin, obtained using widely in the occasion of many outdoor uses.But just because of do not contain two keys in the polyacrylate elastomer, so be difficult to initiation grafting with vinylbenzene, acrylonitrile graft copolymer the time, the result is that percentage of grafting is low, poor impact toughness.In order to overcome this shortcoming, the people is arranged when the preparation of polyacrylate elastomer, add the monomer that contains two two keys and carry out copolymerization, make the elastomerics that obtains have a certain amount of pair of key, in order to grafting.Someone adds organo-peroxide when graft polymerization, improve percentage of grafting and degree of crosslinking.Also there is the people to start with, adopts for a long time continuously the monomeric way of dropping to improve percentage of grafting from the graft process condition.But the mechanical property of commodity AAS resin is still not as good as ABS resin, the raising of percentage of grafting and control, and the improvement of material mechanical performance, be that the AAS resin preparing technical field people difficult point of urgently wishing to solve is (referring to Kohkame H, Shitara M, Tanno S always, Muroi T, Journal of Applied PolymerScience, 46:1775-1784,1992).
The object of the present invention is to provide a kind of preparation that can effectively improve the copolymer grafted rate to have the method for the AAS resin of good mechanical property.
The method for preparing AAS resin that the present invention proposes, its basic step is as follows: when the preparation of polyacrylate elastomer, add the superoxide of the two keys of band in acrylate monomer.Below the decomposition temperature of this superoxide, by the mechanism of radical polymerization, carry out acrylate monomer and the monomeric copolymerization of this superoxide, obtain having the polyacrylate elastomer of peroxide side group.Add grafted monomer vinylbenzene and vinyl cyanide then, system temperature is elevated to the decomposition temperature of peroxide side group, the peroxide side group is decomposed generate macromolecular radical, cause the graft polymerization of vinylbenzene and vinyl cyanide.Change the add-on of superoxide, can regulate the grafting site density of polyacrylate elastomer.Change the add-on of grafted monomer, can regulate total percentage of grafting.Thereby realize controllable graft polymerization.
The used acrylate monomer of preparation polyacrylate elastomer can be one or more of butyl acrylate, ethyl propenoate or acrylic acid other long-chain alkyl groupses.
The molecular structure that the superoxide of the two keys of band that copolymerization is used has following form:
R
1-O-O-R
2
Wherein, R
1And R
2Be two kinds of chemical groups, R
1Contain polymerisable double bonds, R
1With R
2In the part that links to each other with peroxide bridge can be carbonyl or tertiary carbon atom.Below be the example of the superoxide of the two keys of several this bands: CH
2=CHCH
2OC (O)-O-O-tBu t-butylperoxyallyl carbonateCH
2=C (CH
3) C (O) OC
2H
4OC (O)-O-O-tBu t-butylperoxymethacryloyloxyethyl carbonateCH
2=C (CH
3) C
6H
6C (CH
3)
2-O-O-tBu t-butyl-3-isopropenylcumyl peroxideCH
3CH (CH
3) O (O) CCH=CHC (O)-O-O-tBu t-butylperoxyisopropyl formarate
Acrylate monomer can adopt emulsion method, solution method or substance law with the copolymerization of the superoxide of the two keys of band, carries out in the presence of radical initiator.Polymerization temperature should be that 10 hours temperature is low more than 10 ℃ than peroxide bridge half life of decomposition.If polymerization temperature is too high, the peroxide bridge side group that keeps in the polypropylene ester that then obtains is unfavorable for the grafting of back very little.
Acrylate monomer is (both summations are 100) 95: 5～99.7: 0.3 with the ratio of the superoxide of the two keys of band, the superoxide of the two keys of band very little, then embody DeGrain of the present invention, too many words, grafting site density is too high when back and vinylbenzene, acrylonitrile grafting, and impelling strength is with variation.
Graft polymerization can be adopted emulsion method, solution method and substance law.Used grafted monomer mainly is vinylbenzene and vinyl cyanide, also can add following monomeric one or more in addition and come adjusting function: alpha-methyl styrene, methacrylonitrile, N-phenylmaleimide, methyl methacrylate or the like.
The ratio of grafted monomer and polyacrylate elastomer (total amount is 100) was generally 10: 90～80: 20.If the amount of grafted monomer very little, then percentage of grafting is too low, can not guarantee the impelling strength of product.If too much then percentage of grafting is too high, also unfavorable to performance, and also whole preparation process is economical inadequately.
The temperature of graft polymerization is more than 10 hours the temperature 0 ℃ to 60 ℃ at the peroxide bridge half life of decomposition generally.If the temperature of graft polymerization is too low, then polymerization time is oversize.If temperature is too high, then reaction is too fierce, and homopolymer generates more.
The product that graft copolymerization obtains is the AAS of snappiness body burden, passes through the screw extrusion press blend with commodity SAN resin (being two membered copolymers of vinylbenzene and vinyl cyanide) again, just obtains practical AAS resin.According to the different requirements to product properties, the content of the polypropylene ester elastomer in the final blended product can be 14%～25%.The high more then shock resistance of elastomer content is high more, but rigidity, thermotolerance and poor processability.
When extruding blend, screw rod can add various additives as required.For example oxidation inhibitor, ultraviolet absorbers, static inhibitor, fire retardant, lubricant and pigment or the like.
Adopt the percentage of grafting of the AAS resin that method of the present invention obtains to reach 15%～40%, and can control as required.
When polyacrylate elastomer content was 20%, the socle girder notched Izod impact strength can reach more than the 200J/m.
The testing method of percentage of grafting is as follows: get graft polymerization product 0.5 gram, be dispersed in 25 milliliters of acetone, place on the induction stirring platform, stirring and dissolving is 2 hours under room temperature.Get 2 milliliters of suspension, centrifugal settling separates in 12000 rev/mins whizzer, and throw out is made Infrared spectroscopy after separating three times with washing with acetone.Calculate percentage of grafting from typical curve.Percentage of grafting is defined as: the ratio of the weight of grafted styrene/acrylonitrile copolymer and polyacrylate elastomer weight.
The testing method of the shock strength of AAS resin is as follows: with injection moulding AAS resin is processed into 63.5 * 3.17 millimeters strip, processes " V " type breach with milling machine, press GB1843 test cantilever beam impact strength.
Embodiment 1:
Butyl acrylate, ethylene glycol diacrylate and superoxide 1-(2-t-butyl peroxy sec.-propyl)-3-isopropenylbenzene is mixed by 97/2/1 weight ratio, obtain mix monomer.In the three-necked bottle of band prolong, add 200 parts of deionized waters, 1.5 part emulsifier sodium lauryl sulfate and 0.3 part of initiator potassium persulfate, under nitrogen envelope, stir and be warming up to 70 ℃, in 4 hours, splash in the three-necked bottle continuously 100 parts of mix monomers, keep reaction 2 hours at 70 ℃ again, the solid content of the polyacrylate elastomer latex that obtains is 32%, 0.20 micron of particle diameter.
In autoclave pressure, add 120 parts in polyacrylate elastomer glue hole, 220 parts of deionized waters, 44 parts of vinylbenzene, 16 parts of vinyl cyanide, 0.2 part of sodium lauryl sulphate.Airtight behind nitrogen replacement, stir and be warming up to 120 ℃ of reactions 4 hours, transformation efficiency reaches 95%.Cooling discharging with the sal epsom cohesion, washes with water, dries in 70 ℃ of convection oven, obtains the grafting powder of snappiness body burden, and by analysis, its percentage of grafting is 23%.
With 47.6 parts of grafting powder, 0.5 part of oxidation inhibitor B-215,52.4 parts of SAN resins (vinylbenzene that Lan Hua company produces and the copolymer of vinyl cyanide, model HF), 0.4 part of EBS (two hard esteramides) mixes, and uses the twin screw extruder extruding pelletization.After tested, the socle girder notched Izod impact strength of this AAS resin is 214J/m.Embodiment 2:
Utilize the butyl polyacrylate elastomer emulsions of embodiment 1, carry out graft copolymerization.Add 155 parts of this elastomer emulsions, 195 parts of deionized waters, 0.2 part of sodium lauryl sulphate, vinylbenzene and vinyl cyanide are respectively 36.5 parts and 13.5 parts.All the other steps are identical with embodiment 1.Also with SAN elastomer content is diluted to 20% during blend, shock strength is 204J/m as a result.Comparative example 1:
Prepare the butyl polyacrylate elastomer emulsions by the mode similar, just do not add D120 during polymerization, only add butyl acrylate and ethylene glycol diacrylate (98: 2), the emulsion solid content 32.5% that obtains, particle diameter 0.30 μ to embodiment 1.Prescription is similar to embodiment 1 during graft copolymerization, but adds 0.8 part of initiator potassium persulfate, 80 ℃ of reactions 5 hours, and transformation efficiency 95%, by identical method cohesion, washing, drying and blend, shock strength only reaches 15J/m, and percentage of grafting is lower than 7% comparative example 2:
Prepare the butyl polyacrylate elastomer emulsions by the mode similar to embodiment 1.The ratio of butyl acrylate, ethylene glycol diacrylate and D120 changes 98: 2: 0.2 into, and the emulsion solid content that the result measures is 32.5%, particle diameter 0.22 μ.The condition of graft copolymerization is also identical with embodiment 1, but transformation efficiency only reaches 80%.Obtain the grafting powder by identical method cohesion, washing and drying.The ratio of grafting powder and SAN is 47.6: 52.4 during blend, makes the elastomeric content in the blend also remain on 20%, and is identical with embodiment 1.The result is because D120 content is low excessively, and shock strength only reaches 18J/m, and the percentage of grafting of grafting powder is lower than 8%.
Claims (5)
- L, a kind of method for preparing AAS resin when it is characterized in that making each polyacrylate elastomerics, add the superoxide of being with two keys, its molecular architecture: R to acrylate monomer 1-O-O-R 2, R here 1And R 2Be two kinds of chemical groups, wherein R1 contains polymerisable double bonds, R 1And R 2In the part that links to each other with peroxide bridge be carbonyl or tertiary carbon atom, acrylate monomer is 95:5 to 99.7:0.3 with the part by weight of the superoxide of the two keys of band, below the decomposition temperature of this superoxide, mechanism by radical polymerization, carry out acrylate monomer and the monomeric copolymerization of this superoxide, obtain polyacrylate elastomer with the peroxide side group; Add vinylbenzene and acrylonitrile monemer then, system temperature is elevated to the decomposition temperature of peroxide side group, make peroxide survey base and decompose and generate macromolecular radical, cause the graft polymerization of vinylbenzene and vinyl cyanide; Change the add-on of superoxide, regulate the grafting site density of polyacrylate elastomer, change the add-on of grafted monomer, regulate total percentage of grafting, thereby realize controllable graft polymerization, the part by weight of grafted monomer and polyacrylate elastomer is 10:90 to 80:20.
- 2,, it is characterized in that used acrylate monomer is one or more of ethyl propenoate, butyl acrylate or acrylic acid other long-chain alkyl groupses according to the described method for preparing AAS resin of claim l.
- 3, the method for preparing AAS resin according to claim 2, it is that lO hour temperature is low more than 10 ℃ that the temperature that it is characterized in that acrylate monomer and the superoxide copolymerization of the two keys of band decomposed for half rate phase than peroxide bridge.
- 4, the method for preparing AAS resin according to claim 3, it is characterized in that adding in addition following monomeric one or more: α monomethyl vinylbenzene, methacrylonitrile, methyl methacrylate, N one phenyl maleimide.
- 5, the method for preparing AAS resin according to claim 4, the temperature that it is characterized in that graft polymerization more than lO hour temperature of peroxide bridge half life of decomposition 0 ℃ to 60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121931A CN1073577C (en) | 1998-09-30 | 1998-09-30 | Process for preparing acrylonitrile, phenylethylene and polyacrylate graft copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121931A CN1073577C (en) | 1998-09-30 | 1998-09-30 | Process for preparing acrylonitrile, phenylethylene and polyacrylate graft copolymer |
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| Publication Number | Publication Date |
|---|---|
| CN1223272A CN1223272A (en) | 1999-07-21 |
| CN1073577C true CN1073577C (en) | 2001-10-24 |
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|---|---|---|---|
| CN98121931A Expired - Fee Related CN1073577C (en) | 1998-09-30 | 1998-09-30 | Process for preparing acrylonitrile, phenylethylene and polyacrylate graft copolymer |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004067789A (en) * | 2002-08-05 | 2004-03-04 | Sumitomo Chem Co Ltd | Method for manufacturing cast molded article of impact-resistant methacrylate resin |
| US20040225034A1 (en) * | 2003-05-09 | 2004-11-11 | General Electric Company | Impact-modified compositions and method |
| US20090121370A1 (en) * | 2007-10-26 | 2009-05-14 | Bausch & Lomb Incorporated | Molds for Production of Ophthalmic Devices |
| CN102344635B (en) * | 2010-08-05 | 2013-10-16 | 中国石油天然气股份有限公司 | Preparation method of weather resistant and impact resistant modified resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4397992A (en) * | 1982-04-21 | 1983-08-09 | Wyrough And Loser, Inc. | Predispersed liquid or low melting solid peroxide vulcanizing agent or coagent compositions |
| CN1169740A (en) * | 1994-11-14 | 1998-01-07 | 巴斯福股份公司 | Process for producing modified rubber moulding masses by using peroxy group-containing compounds |
-
1998
- 1998-09-30 CN CN98121931A patent/CN1073577C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4397992A (en) * | 1982-04-21 | 1983-08-09 | Wyrough And Loser, Inc. | Predispersed liquid or low melting solid peroxide vulcanizing agent or coagent compositions |
| CN1169740A (en) * | 1994-11-14 | 1998-01-07 | 巴斯福股份公司 | Process for producing modified rubber moulding masses by using peroxy group-containing compounds |
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|---|---|
| CN1223272A (en) | 1999-07-21 |
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