CN1590424A - Acrylic ester core-shell polymer - Google Patents
Acrylic ester core-shell polymer Download PDFInfo
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- CN1590424A CN1590424A CN 03150731 CN03150731A CN1590424A CN 1590424 A CN1590424 A CN 1590424A CN 03150731 CN03150731 CN 03150731 CN 03150731 A CN03150731 A CN 03150731A CN 1590424 A CN1590424 A CN 1590424A
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Abstract
A core-shell polymer of acrylate with high adhesive between core and shell for modifying polyvinyl chloride features that the alkyl acrylate is used as its core, methyl methylacrylate is used as its shell, and the alkyl acrylate-methyl methylacrylate is used to link core with shell.
Description
Technical field
The present invention relates to a kind of acrylate core-shell polymer, particularly about between its nuclear and shell, there being the acrylate core-shell polymer of nuclear and shell monomer multipolymer compatilizer.
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 the core-shell material that makes in the conventional art, because the consistency between nuclear and the shell is bad, cause the bonding force between the nucleocapsid poor, during with this core-shell material modified polyvinyl chloride blend, the problem that the impact property of blend is not good provides a kind of new acrylate core-shell polymer.During this polymer modification polyvinyl chloride, have the advantages that significantly to improve the polyvinyl chloride 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 acrylate core-shell polymer comprises following component 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.
In the technique scheme, acrylate core-shell polymer preferred version is for containing nuclear and shell, its center is acrylic acid alkyl ester polymer and compatilizer, and 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 by weight percentage contains 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.Bifunctional monomer in the acrylic acid alkyl ester polymer more preferably scheme is a hexanediol diacrylate.The methyl methacrylate polymer preferred version is imperplex or multipolymer.The dynamic mechanics heat analysis spectrogram of acrylate core-shell polymer is presented at also has a low broad peak between 0 ℃～50 ℃, this broad peak is the second-order transition temperature of compatilizer alkyl acrylate-methylmethacrylate copolymer.Alkyl acrylate-methylmethacrylate copolymer preferred version by weight percentage comprises following component:
A) 30～70% acrylic acid alkyl ester units;
B) 30～70% methyl methacrylate units.
Methyl methacrylate polymer preferred version by weight percentage comprises following component:
A) 70% to 100% methyl methacrylate units;
B) 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;
C) 0 to 30% comonomer unit, comonomer are selected from least a in vinyl cyanide, methacrylonitrile, vinylbenzene or the alpha-methyl styrene.
The vinyl chloride-base polymer that uses 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 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.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.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.Adopt coagulating wadding method or spray drying process in addition separates from acrylate core-shell polymer latex and obtains the acrylate core-shell polymer.
According to the present invention, in fact the acrylate core-shell polymer comprises nuclear, nuclear/shell monomer and shell, and this three stratas compound has different second-order transition temperatures respectively.The dynamic mechanical loss tangent Tan δ that obtains by dynamic mechanics heat analysis and the curve of temperature, except respectively having a peak value to represent respectively nuclear (rubber phase) and the shell second-order transition temperature of (plastics mutually) with about-128 ℃ at-21 ℃, also have a low broad peak between 0 ℃～50 ℃, this broad peak is the second-order transition temperature of nuclear/shell monomer multipolymer.
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 impact modified polyvinyl chloride blend among 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 nuclear and 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, 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, because the introducing of this nuclear and shell monomer multipolymer can be adopted the continuous charging mode to shell monomers, make exothermic heat of reaction steady simultaneously, 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.
Description of drawings
Fig. 1, Fig. 2 are respectively the dynamic mechanics heat analysis spectrograms of the vinylformic acid core-shell polymer of the embodiment of the invention 1 and 2.
Fig. 3 is the dynamic mechanics heat analysis spectrogram of the vinylformic acid core-shell polymer of prior art comparative example 1.
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 1,000 0.6% (weight) calcium chloride waters that restrain of high-speed stirring under 200 gram acrylate core-shell polymer latex (C) room temperatures, then with this mixture heating up to 80 ℃, kept 30 minutes, 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
High-efficiency compound stabilizer XH5702 3.8phr
ACR?401???????????????????????????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.On two rollers, carry out this dry blend mixing, two roll temperatures are 175 ± 5 ℃, mixing time 12 minutes, then 185 ℃ of following hot pressing 4 minutes, the sample of preparation is tested its simple beam impact strength by the requirement of ISO179, The performance test results sees Table 1, and the dynamic mechanics heat analysis spectrogram of its acrylate core-shell polymer is seen Fig. 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, and the dynamic mechanics heat analysis spectrogram of its acrylate core-shell polymer is seen Fig. 2.
[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, and the dynamic mechanics heat analysis spectrogram of its acrylate core-shell polymer is seen Fig. 3.
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 (8)
1, a kind of acrylate core-shell polymer comprises following component 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, according to the described acrylate core-shell polymer 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.
3,, it is characterized in that the acrylic acid alkyl ester polymer has by weight percentage with lower unit according to the described acrylate core-shell polymer 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.
4,, it is characterized in that the bifunctional monomer unit in the acrylic acid alkyl ester polymer is a hexanediol diacrylate according to the described acrylate core-shell polymer of claim 3.
5,, it is characterized in that methyl methacrylate polymer is imperplex or multipolymer according to the described acrylate core-shell polymer of claim 1.
6, according to the described acrylate core-shell polymer of claim 1, the dynamic mechanics heat analysis spectrogram that it is characterized in that the acrylate core-shell polymer is presented at also has a low broad peak between 0 ℃～50 ℃, this broad peak is the second-order transition temperature of compatilizer alkyl acrylate-methylmethacrylate copolymer.
7,, it is characterized in that alkyl acrylate-methylmethacrylate copolymer comprises following component by weight percentage according to the described acrylate core-shell polymer of claim 1:
A) 30～70% acrylic acid alkyl ester units;
B) 30～70% methyl methacrylate units.
8,, it is characterized in that methyl methacrylate polymer comprises following component by weight percentage according to the described acrylate core-shell polymer of claim 1:
A) 70% to 100% methyl methacrylate units;
B) 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;
C) 0 to 30% comonomer unit, comonomer are selected from least a in vinyl cyanide, methacrylonitrile, vinylbenzene or the alpha-methyl styrene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150731 CN1245427C (en) | 2003-09-03 | 2003-09-03 | Acrylic ester core-shell polymer |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03150731 CN1245427C (en) | 2003-09-03 | 2003-09-03 | Acrylic ester core-shell polymer |
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| CN1245427C CN1245427C (en) | 2006-03-15 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418065B (en) * | 2007-10-23 | 2010-11-17 | 山东瑞丰高分子材料股份有限公司 | Impact modifier applied to PVC bellow |
| CN102453291A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Anti-impact polyvinyl chloride composition and preparation method thereof |
| EP2308909A4 (en) * | 2008-07-31 | 2016-08-03 | Daicel Chem | Optical semiconductor sealing resin composition and optical semiconductor device using same |
| CN105968315A (en) * | 2016-05-16 | 2016-09-28 | 常州大学 | Preparation method of polymethyl-methacrylate-based compatilizer |
-
2003
- 2003-09-03 CN CN 03150731 patent/CN1245427C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418065B (en) * | 2007-10-23 | 2010-11-17 | 山东瑞丰高分子材料股份有限公司 | Impact modifier applied to PVC bellow |
| EP2308909A4 (en) * | 2008-07-31 | 2016-08-03 | Daicel Chem | Optical semiconductor sealing resin composition and optical semiconductor device using same |
| CN102453291A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Anti-impact polyvinyl chloride composition and preparation method thereof |
| CN102453291B (en) * | 2010-10-25 | 2013-11-06 | 中国石油化工股份有限公司 | Anti-impact polyvinyl chloride composition and preparation method thereof |
| CN105968315A (en) * | 2016-05-16 | 2016-09-28 | 常州大学 | Preparation method of polymethyl-methacrylate-based compatilizer |
| CN105968315B (en) * | 2016-05-16 | 2018-06-08 | 常州大学 | A kind of preparation method based on polymethyl methacrylate compatilizer |
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| Publication number | Publication date |
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| CN1245427C (en) | 2006-03-15 |
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