CN1611540A - Impact-modified poly vinyl chloride polymer blend - Google Patents
Impact-modified poly vinyl chloride polymer blend Download PDFInfo
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- CN1611540A CN1611540A CN 200310108169 CN200310108169A CN1611540A CN 1611540 A CN1611540 A CN 1611540A CN 200310108169 CN200310108169 CN 200310108169 CN 200310108169 A CN200310108169 A CN 200310108169A CN 1611540 A CN1611540 A CN 1611540A
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Abstract
The invention relates to a kind of polyvinyl-chlorid blend with impact modification. The invention mainly solves the problem that bad compatibility and bad binding force of nucleus and shell cause the bad impact property of polyvinyl-chlorid blend with impact modification in modifying polyvinyl-chlorid with putamen material by previous technology. In the invention, use acrylic acid carbalkoxy polymer and acrylic acid carbalkoxy-methyl methacrylate copolymer compatiblizing agent as nucleus, use methyl methacrylate as shell, and nucleus-shell are connected with compatiblizing agent. The invention can solve the problems mentioned above through the technical proposal of impact modification polyvinyl-chlorid with acrylate putamen polymer described above, and it can be used in industrial production.
Description
Technical field
The present invention relates to a kind of impact modified polyvinyl chloride blend, particularly about with the polyvinyl chloride blend of acrylate core-shell polymer as impact modifying agent.
Background technology
Polyvinyl chloride is used widely owing to its good mechanical property and chemical property, yet polyvinyl chloride (PVC) RESINS itself is owing to the shock resistance difference thereby need the adding impact modifying agent improve its impact property, what application was more at present is methyl methacrylate-butadiene-styrene graft copolymer (MBS), but because the two keys among the MBS make it degraded easily under UV-irradiation, impact property descends morely when being used for the open air for a long time with the polyvinyl chloride of MBS modification, and weathering resistance is poor.What the weatherability polyvinyl chloride impact modifying agent generally adopted is the acrylate core-shell polymer, and has been widely used in the outdoor application such as tubing, sheet material and window frame.Nineteen fifty-seven Rohm ﹠amp; Haas company reported first use the acrylate core-shell polymer of acrylic acid alkyl ester polymer for nuclear.In general, its nuclear of the acrylate core-shell polymer of weather resisteant is crosslinked acrylic acid alkyl ester polymer (rubber phase), and shell is methyl methacrylate polymer (a plastics phase).Because consistency is bad between acrylic acid alkyl ester polymer and the methyl methacrylate polymer, therefore want the good acrylate core-shell polymer of obtained performance, key is the bonding force that will improve between nuclear and the shell, just will improve the bonding force between rubber phase and the plastics phase.Reported among the CN1178227 and a kind ofly made rubber phase and plastics form one deck interpenetrating net polymer between mutually by the control swelling time of shell monomers in rubber latex to improve rubber rubber phase and the plastics bonding force between mutually, but because shell monomers is disposable adding, monomer concentration is big thereby polymerization rate is also big, might cause system temperature sharply to rise and wayward.Having introduced a kind of method among the US4670509 adopts and contains the active bifunctional vinyl compound of differential responses such as allyl methacrylate(AMA) as linking agent, increase the grafting degree of plastics phase, improve rubber phase and the plastics bonding force between mutually with this, but its shell monomers also is disposable adding.
Summary of the invention
Technical problem to be solved by this invention is in the conventional art, during with the core-shell material modified polyvinyl chloride, because the consistency between nuclear and the shell is bad, bonding force between the nucleocapsid is poor, cause the not good problem of polyvinyl chloride blend impact property of its modification, a kind of new impact modified polyvinyl chloride blend is provided.This blend has the characteristics of good impact property.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of impact modified polyvinyl chloride blend, and meter comprises following component by weight:
1) 100 parts of vinyl chloride-base polymers;
2) 2～30 parts of acrylate core-shell polymers, this acrylate core-shell polymer comprises following composition by weight percentage:
A) 65% to 85% acrylic acid alkyl ester polymer;
B) compatilizer of alkyl acrylate-methylmethacrylate copolymer of 1% to 5%;
C) 10% to 30% methyl methacrylate polymer.
The preferred version of vinyl chloride-base polymer is a ryuron in the technique scheme.Acrylate core-shell polymer preferred version for contain nuclear and shell, its center is acrylic acid alkyl ester polymer and compatilizer, shell is a methyl methacrylate polymer, nuclear with shell between link to each other by compatilizer alkyl acrylate-methylmethacrylate copolymer.Acrylic acid alkyl ester polymer preferred version is for containing by weight percentage with lower unit:
A) 80% to 99.5% butyl acrylate units;
B) 0 to 19.5% comonomer unit;
C) 0.5% to 5% bifunctional monomer unit;
Wherein comonomer is selected from least a in ethyl propenoate, propyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Octyl acrylate or the 2-EHA; The bifunctional monomer is selected from least a in Vinylstyrene, allyl methacrylate, vinylformic acid allyl ester, ethylene glycol diacrylate, diacrylate propylene glycol ester, diacrylate butanediol ester, hexanediol diacrylate, Ethylene glycol dimethacrylate, dimethyl allene acid propylene glycol ester, tetramethylene dimethacrylate, dimethacrylate hexylene glycol ester, trimethyol propane triacrylate or the trihydroxy methyl propane trimethyl acrylate, and preferred version is a hexanediol diacrylate.
Vinyl chloride-base polymer among the present invention is not limited in polyvinyl chloride homopolymer, also can be the multipolymer of vinylchlorid and vinyl monomer, these vinyl monomers can be alkyl acrylate, alkyl methacrylate, vinylbenzene, alpha-methyl styrene, vinyl cyanide, dialkyl maleate, N-substituted maleimide amine, vinyl-acetic ester etc.
The preparation method of the acrylate core-shell polymer that uses among the present invention adopts seeded emulsion polymerization technology, at first make partial cross-linked alkyl acrylate polymer latex (nuclear), on this latex, form the copolymer layer (compatilizer) of alkyl acrylate and methyl methacrylate then, on this copolymer layer, form methyl methacrylate polymer (shell) at last and obtain acrylate core-shell polymer latex.Can adopt with fixed attention wadding method or spray drying process from acrylate core-shell polymer latex, to separate and obtain the acrylate core-shell polymer.
Among the present invention, behind preparation alkyl acrylate polymer rubber nuclear, further form the multipolymer of alkyl acrylate-methyl methacrylate on this rubbery kernel basis, this multipolymer covers on the alkyl acrylate polymer rubber nuclear equably.Alkyl acrylate-methylmethacrylate copolymer comprises by weight percentage:
(1) 30% to 70% butyl acrylate units;
(2) 70% to 30% methyl methacrylate units.
According to the present invention, on alkyl acrylate-methylmethacrylate copolymer, form methyl methacrylate polymer at last, cover the surface of alkyl acrylate-methylmethacrylate copolymer equably.Methyl methacrylate polymer comprises by weight percentage:
(1) 70% to 100% methyl methacrylate units;
(2) 0 to 2% bifunctional monomer unit, the bifunctional monomer is selected from least a in Vinylstyrene, allyl methacrylate, vinylformic acid allyl ester, ethylene glycol diacrylate, diacrylate propylene glycol ester, diacrylate butanediol ester, hexanediol diacrylate, Ethylene glycol dimethacrylate, dimethyl allene acid propylene glycol ester, tetramethylene dimethacrylate, dimethacrylate hexylene glycol ester, trimethyol propane triacrylate or the trihydroxy methyl propane trimethyl acrylate;
(3) 0 to 30% comonomer unit, comonomer are selected from least a in vinyl cyanide, methacrylonitrile, vinylbenzene, the alpha-methyl styrene.
According to the present invention, when the preparation methyl methacrylate polymer, the feed way of methyl methacrylate monomer can adopt the continuous charging mode, makes the polyreaction heat release steady, and polymerization process is controlled easily, is easy to amplify.
According to the present invention, can adopt with fixed attention wadding method or spray drying process from acrylate core-shell polymer latex, to separate and obtain the acrylate core-shell polymer.
Acrylate core-shell polymer of the present invention is used for the impact modified very effective of polyvinyl chloride and multipolymer thereof, the polyvinyl chloride blend of gained can comprise one or more thermo-stabilizers, can be one package stabilizer, organo-tin compound, organo-lead compound, barium cadmium organic salt, calcium zn cpds etc., preferred version be an one package stabilizer.Also can comprise lubricant such as paraffin, olefin polymer and comprise being used to promote fused processing aid such as high-molecular weight alkylmethacrylate polymer, also can comprise tinting material and filler etc. in addition.
Also can be used for the impact modified of engineering plastics such as polyester, polycarbonate etc. add oxidation inhibitor and thermo-stabilizer in the acrylate core-shell polymer after, typical oxidation inhibitor and thermo-stabilizer have hindered phenol, aromatic amine compound, phosphorous acid esters and sulfur ester.
The preparation method of the impact modified polyvinyl chloride blend of the present invention, after employing mixes raw material stirring earlier, mixing forming on two rollers.
Its nuclear of acrylate core-shell polymer is crosslinked acrylic acid alkyl ester polymer (rubber phase), shell is methyl methacrylate polymer (a plastics phase), because consistency is bad between acrylic acid alkyl ester polymer and the methyl methacrylate polymer, therefore the polyvinyl chloride blend that has the acrylate core-shell polymer modification of simple core/shell structure tends to when being subjected to external impacts owing to acrylate core-shell polymer center and the decline that causes the polyvinyl chloride blend impact property separating of shell, so the structure of acrylate core-shell polymer is most important to the impact property of polyvinyl chloride blend.Want the good acrylate core-shell polymer of obtained performance, key is the bonding force that will improve between nuclear and the shell, just will improve the bonding force between rubber phase and the plastics phase.The inventor is by forming a nuclear and a shell monomer copolymer layer as the acrylic acid alkyl ester polymer of nuclear with between as the methyl methacrylate polymer of shell, as the compatilizer between nuclear and the shell, improved the bonding force between nuclear and the shell, simultaneously because the introducing of this nuclear and shell multipolymer, can adopt the continuous charging mode to shell monomers, make exothermic heat of reaction steady, polymerization process is controlled easily, is easy to amplify.Adopt this impact modifying agent modified polyvinyl chloride alkene polymer, the blend of acquisition has had good impact property, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
1) preparation of acrylic acid alkyl ester polymer
In the polymeric kettle that thermometer, agitator, nitrogen gatherer and monomer addition device are housed, add 800 gram deionized waters, 0.5 gram Sodium dodecylbenzene sulfonate, 80 gram butyl acrylates, 2 gram hexanediol diacrylate.Stir and down reactant is warming up to 70 ℃, and feed nitrogen continuously.After reaction causes, add the pre-emulsion that contains 800 gram deionized waters, 10 gram Sodium dodecylbenzene sulfonatees, 680 gram butyl acrylates, 18 gram hexanediol diacrylate and 7.5 gram ammonium persulphates continuously, add in about 2 hours.After dropwising, continue reaction 2 hours, getting particle diameter is the alkyl acrylate polymer latex (A) of 200 nanometers.
2) preparation of the multipolymer of alkyl acrylate-methyl methacrylate
In above-mentioned latex (A), add 0.3 gram ammonium persulphate, disposable adding 20 gram butyl acrylates and 20 gram methyl methacrylates, reacted 2 hours, and obtained the alkyl acrylate polymer latex (B) that surface coverage has butyl acrylate-methylmethacrylate copolymer.
3) preparation of methyl methacrylate polymer
In above-mentioned latex (B), add 100 1% (weight) sodium dodecyl benzene sulfonate aqueous solutions (1% weight) that restrain and 1 gram ammonium persulphate, add 180 gram methyl methacrylates continuously, add in about 2 hours, system temperature rises to 80 ℃ with system temperature after having fed in raw material and continues reaction 2 hours owing to about 2 ℃ of exothermic heat of reaction peak temperature rise in reinforced process.Finish reaction, be cooled to 40 ℃, filter, obtain acrylate core-shell polymer latex (C).
4) separation of acrylate core-shell polymer
To be added drop-wise in the 1000 0.6% weight calcium chloride waters that restrain of high-speed stirring under 200 gram acrylate core-shell polymer latex (C) room temperatures, with this mixture heating up to 80 ℃, kept 30 minutes then, filter, the water flushing is carried out drying and is obtained the white powder solid under 90 ℃ of conditions.
Also can adopt spray drying process from acrylate core-shell polymer latex (C), to separate and obtain the acrylate core-shell polymer, spray condition: 140～160 ℃ of inlet air temperature, 80 ℃ of air outlet temperatures.
5) preparation of polyvinyl chloride blend
Polyvinyl chloride blend representative formula as follows:
PVC homopolymer (mean polymerisation degree 1000) 100phr
One package stabilizer XH5702 3.8phr
ACR401?????????????????????????1.8phr
Lightweight CaCO
39phr
TiO
2??????????????????????????4phr
Acrylate core-shell polymer 5phr
Phr: the umber of per hundred parts of resins.
The device high speed that said components is joined in certain sequence high-speed stirring mixes, and is heated to 118 ℃, and cooling obtains the polyvinyl chloride dry blend.This dry blend is carried out mixing on two rollers, two roll temperatures are 175 ± 5 ℃, mixing time 12 minutes, and 185 ℃ of following hot pressing 4 minutes, the sample of preparation was tested its simple beam impact strength by the requirement of ISO179 then, and The performance test results sees Table 1.
[embodiment 2]
Preparation technology is similar to embodiment 1, just process 3) add-on of methyl methacrylate is 247 grams in the preparation of methyl methacrylate polymer.Peak temperature rise is about 3 ℃ in this process.
This routine prepared acrylate core-shell polymer is prepared polyvinyl chloride blend by preparation technology among the embodiment 1, and The performance test results sees Table 1
[comparative example 1]
Remove the preparation process of the multipolymer of alkyl acrylate-methyl methacrylate among the preparation technology of embodiment 1, after making the alkyl acrylate polymer latex, directly carry out the preparation of methyl methacrylate polymer, correspondingly incorporate gram butyl acrylate of 20 in the preparation process of the multipolymer of alkyl acrylate-methyl methacrylate among the embodiment 1 and 20 gram methyl methacrylates into the preparation process (promptly participating in pre-emulsified butyl acrylate is 700 grams) of acrylic acid alkyl ester polymer and the preparation process (being that the methyl methacrylate add-on is 200 grams) of methyl methacrylate polymer respectively.
Peak temperature rise is about 2 ℃ in the preparation process of methyl methacrylate polymer.
This routine prepared acrylate core-shell polymer is prepared polyvinyl chloride blend by preparation technology among the embodiment 1, and The performance test results sees Table 1
Table 1
| Acrylate core-shell polymer weight percent is formed (%) | Simply supported beam notched Izod impact strength (the kilojoule/rice of polyvinyl chloride blend 2) | Peak temperature rise in the preparation process of methyl methacrylate polymer (℃) | |||
| Nuclear | Nuclear/shell multipolymer (linking agent) | Shell | |||
| Embodiment 1 | ????78 | ????4 | ????18 | ????110 | ??2 |
| Embodiment 2 | ????73 | ????4 | ????23 | ????98 | ??3 |
| Comparative example 1 | ????80 | ????20 | ????82 | ??2 | |
Claims (5)
1, a kind of impact modified polyvinyl chloride blend, meter comprises following component by weight:
1) 100 parts of vinyl chloride-base polymers;
2) 2～30 parts of acrylate core-shell polymers, this acrylate core-shell polymer comprises following composition by weight percentage:
A) 65% to 85% acrylic acid alkyl ester polymer;
B) compatilizer of alkyl acrylate-methylmethacrylate copolymer of 1% to 5%;
C) 10% to 30% methyl methacrylate polymer.
2,, it is characterized in that vinyl chloride-base polymer is a ryuron according to the described impact modified polyvinyl chloride blend of claim 1.
3, according to the described impact modified polyvinyl chloride blend of claim 1, it is characterized in that the acrylate core-shell polymer contains nuclear and shell, its center is acrylic acid alkyl ester polymer and compatilizer, shell is a methyl methacrylate polymer, nuclear with shell between link to each other by compatilizer alkyl acrylate-methylmethacrylate copolymer.
4,, it is characterized in that the acrylic acid alkyl ester polymer contains by weight percentage with lower unit according to the described impact modified polyvinyl chloride blend of claim 1:
A) 80% to 99.5% butyl acrylate units;
B) 0 to 19.5% comonomer unit;
C) 0.5% to 5% bifunctional monomer unit;
Wherein comonomer is selected from least a in ethyl propenoate, propyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Octyl acrylate or the 2-EHA; The bifunctional monomer is selected from least a in Vinylstyrene, allyl methacrylate, vinylformic acid allyl ester, ethylene glycol diacrylate, diacrylate propylene glycol ester, diacrylate butanediol ester, hexanediol diacrylate, Ethylene glycol dimethacrylate, dimethyl allene acid propylene glycol ester, tetramethylene dimethacrylate, dimethacrylate hexylene glycol ester, trimethyol propane triacrylate or the trihydroxy methyl propane trimethyl acrylate.
5,, it is characterized in that the bifunctional monomer unit in the acrylic acid alkyl ester polymer is a hexanediol diacrylate according to the described impact modified polyvinyl chloride blend of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108169 CN1245448C (en) | 2003-10-27 | 2003-10-27 | Impact-modified poly vinyl chloride polymer blend |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108169 CN1245448C (en) | 2003-10-27 | 2003-10-27 | Impact-modified poly vinyl chloride polymer blend |
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| CN1611540A true CN1611540A (en) | 2005-05-04 |
| CN1245448C CN1245448C (en) | 2006-03-15 |
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| CN 200310108169 Expired - Fee Related CN1245448C (en) | 2003-10-27 | 2003-10-27 | Impact-modified poly vinyl chloride polymer blend |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109071906A (en) * | 2016-04-20 | 2018-12-21 | 罗门哈斯公司 | polyvinyl chloride pipe |
| CN109608584A (en) * | 2018-12-14 | 2019-04-12 | 无锡洪汇新材料科技股份有限公司 | A kind of vinyl chloride multi-copolymerization resin and preparation method thereof |
-
2003
- 2003-10-27 CN CN 200310108169 patent/CN1245448C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109071906A (en) * | 2016-04-20 | 2018-12-21 | 罗门哈斯公司 | polyvinyl chloride pipe |
| CN109608584A (en) * | 2018-12-14 | 2019-04-12 | 无锡洪汇新材料科技股份有限公司 | A kind of vinyl chloride multi-copolymerization resin and preparation method thereof |
| CN109608584B (en) * | 2018-12-14 | 2021-05-11 | 无锡洪汇新材料科技股份有限公司 | Vinyl chloride multi-component copolymer resin and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1245448C (en) | 2006-03-15 |
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