CN1919888A - Preparation method for modifier of poly n-butyl acrylate plastic - Google Patents
Preparation method for modifier of poly n-butyl acrylate plastic Download PDFInfo
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- CN1919888A CN1919888A CN 200510041581 CN200510041581A CN1919888A CN 1919888 A CN1919888 A CN 1919888A CN 200510041581 CN200510041581 CN 200510041581 CN 200510041581 A CN200510041581 A CN 200510041581A CN 1919888 A CN1919888 A CN 1919888A
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Abstract
The invention discloses a method to prepare poly (methyl) acroleic acid butyre plastic modifier, which comprises the following steps: A. forming small grain size graft main latex; B. expanding graft main latex grain size; B1, forming agglomeration latex; B2, expanding agglomeration; C. aggregating graft, getting plastic modifier of acroleic acid butyre rubber as core and rigid monomer as case.
Description
Technical field
The present invention relates to a kind of preparation method of rubber graft copolymer, especially the preparation method of butyl polyacrylate (PBA) plastic modifier belongs to the chemical industry technical field.
Background technology
Understand according to the applicant, the latex particle size amplification method in butyl polyacrylate (PBA) the plastic modifier preparation process has 4 kinds:
1, amplify particle diameter by control emulsifying agent consumption, this method gained PBA latex particle size can only reach about 140 nanometers;
2, polyelectrolyte enlarges particle diameter, and from the letex polymerization theory as can be known, along with the ionogen consumption increases, total trend is that latex particle size becomes greatly, but Na ion concentration increases in the system, has reduced the electric charge on micelle surface, and colloidal particle stability is descended;
3, seeding polymerization method: earlier synthetic seed latex, based on seed latex, drip monomer and emulsifying agent in batches or continuously, particle is increased, this method is more advanced, but the bad control of particle diameter;
4, seed latex multistep diameter expansion method, this method complex steps, long reaction time.
In addition, retrieval is found, the Chinese invention patent application that application number is 98121443, the applying date is on October 30th, 1998 discloses the manufacture method of poly-(methyl) alkyl acrylate latex, and with it as the anti-impact modifier in the thermoplastic resin molded composition of graft copolymer.Though this method is the particle diameter of controlling polymers to a certain extent, the particle diameter instability of polymkeric substance, the molecular weight of batch production product is inconsistent.
Summary of the invention
The objective of the invention is to: at the problem that above prior art exists, by the improvement to butyl polyacrylate latex particle size amplification method, it is simple and direct to propose a kind of technology, particle diameter preparation method for modifier of poly n-butyl acrylate plastic stable, that control easily.
In order to reach above purpose, preparation method for modifier of poly n-butyl acrylate plastic of the present invention may further comprise the steps:
A, synthetic small particle size grafting trunk latex
Butyl acrylate, cross-linking monomer and auxiliary material monomer are mixed, and three's proportionlity is advisable with following weight percent usually: butyl acrylate 70-99.9%, cross-linking monomer 0.1-10%, auxiliary material monomer 0-29%; Add corresponding emulsifying agent, initiator, conditioning agent and medium; Above each material is added in the reactor; Temperature is the 60-85 degree in the controlling reactor, reaction times 4-6 hour; Measure transformation efficiency and reach 95%, discharging during PH=6.0; Make small particle size grafting trunk latex, particle diameter is generally the 60-110 nanometer;
B, the hole enlargement of grafting trunk latex particle
B1, synthetic agglomerating latex---butyl acrylate is mixed with α, beta-unsaturated carboxylic acid (methacrylic acid or vinylformic acid), usually butyl acrylate 70-90%, α, beta-unsaturated carboxylic acid (methacrylic acid or vinylformic acid) 10-30% are advisable, and add corresponding emulsifying agent, initiator, conditioning agent and medium, above each material is added reactor, temperature is the 60-85 degree in the controlling reactor, reaction times 4-6 hour, transformation efficiency reached discharging in 98% o'clock.Make agglomerating latex.
B2, agglomeration hole enlargement---under 17-45 ℃ of temperature condition, agglomerating latex is added in the small particle size grafting trunk latex, both proportionlitys are agglomerating latex 0.5-5%, small particle size grafting trunk latex 95-99.5%, 30 seconds-30 minutes joining day (being preferably 30 seconds), stir (churning time is generally 3 minutes to 1 hour), make it the agglomeration hole enlargement, make the big particle diameter grafting trunk latex through the agglomeration hole enlargement, particle diameter can reach the 250-500 nanometer; (before the agglomeration, can in small particle size grafting trunk latex, add small amount of electrolyte, make agglomeration rapider.)
C, graft polymerization
To add through the big particle diameter grafting trunk latex of agglomeration hole enlargement in the reactor, (its proportionlity is vinylbenzene 50-100% with grafted monomer vinylbenzene and the monomeric mixture of at least a auxiliary material, auxiliary material monomer 0-50%) adds reactor, proportionlity through the mixture of the big particle diameter grafting trunk latex of agglomeration hole enlargement and vinylbenzene and auxiliary material monomer is, big particle diameter grafting trunk latex 20 to 70% through the agglomeration hole enlargement, the mixture 30 to 80% of vinylbenzene and auxiliary material monomer, the mixture of vinylbenzene and auxiliary material monomer adds at twice, make the micelle swelling, twice adds pitch time is 0.8-1.2 hour, in reactor, add corresponding required emulsifying agent during reaction, initiator, conditioning agent and medium, 60-85 ℃ was reacted 4-8 hour down, the cooling discharging, with calcium chloride solution cohesion, dehydration, washing, it is nuclear that drying makes with the butyl acrylate rubber, hard monomer (vinylbenzene and the monomeric mixture of at least a auxiliary material) is the plastic modifier white powder of shell.
Below all be weight percentage.
Action of evocating is for providing free radical; Acting as of emulsifying agent provides micella, forms emulsion; Acting as of conditioning agent produces chain transfer, control molecular weight.
Cross-linking monomer in the above-mentioned grafting trunk is a kind of in Vinylstyrene, cyanuric acid alkatriene third fat, glycidyl methacrylate, O-phthalic base diallyl, the Ethylene glycol dimethacrylate.
Auxiliary material monomer in the above-mentioned grafting trunk is a kind of in vinylbenzene, methyl methacrylate, the ethyl propenoate or two kinds.
Above-mentioned grafting auxiliary material monomer is vinyl cyanide, methyl methacrylate, glycidyl methacrylate, amides monomer.
Experimental results show that, because method of the present invention adopts the polymer latex agglomeration technique to enlarge the PBA latex particle size, latex after the hole enlargement is directly used in graft polymerization, and employing redox system initiated polymerization, therefore compared with prior art, technology is very simple and direct, and the size of particle diameter can be by agglomerating latex dosage and the artificial control of agglomeration time, the product batches differences is very little, is convenient to suitability for industrialized production.
Embodiment
Embodiment one
The preparation method for modifier of poly n-butyl acrylate plastic of present embodiment
1, synthetic small particle size grafting trunk latex:
With butyl acrylate 99.9%, cross-linking monomer cyanuric acid alkatriene third fat 0.1%, auxiliary material monomer are zero; With butyl acrylate+cyanuric acid alkatriene third fat+auxiliary material monomer=1, corresponding adding emulsifying agent, initiator, conditioning agent and medium, emulsifier sodium lauryl sulfate 0.35%; Initiator potassium persulfate 0.5%, conditioning agent mercaptan 0.3%; Medium deionized water 200%.By above proportioning each material is added in the reactor, control reaction temperature is 75 degree, in 5 hours reaction times, measures transformation efficiency and reaches 95%, discharging during PH=6.0.Synthetic small particle size grafting trunk latex.
2, grafting trunk latex particle hole enlargement
2.1, synthetic agglomerating latex
Butyl acrylate 85%, α, beta-unsaturated carboxylic acid are vinylformic acid, vinylformic acid 15%; With butyl acrylate+vinylformic acid=1, corresponding adding emulsifying agent, initiator and medium, emulsifier sodium lauryl sulfate 0.5%, initiator potassium persulfate 0.35%, medium deionized water 160% (control solid content≤40%).By above proportioning each material is added reactor, control reaction temperature 70 degree, 5 hours reaction times, discharging.Make agglomerating latex.
2.2, the agglomeration hole enlargement
The small particle size grafting trunk latex (doing) 98% of step 1 gained, the agglomerating latex 2% of step 2.1 gained carries out agglomeration reaction after the mixing, make the big particle diameter grafting trunk latex through the agglomeration hole enlargement, and particle diameter is about 350 nanometers.
3, graft polymerization
To add through the big particle diameter grafting trunk latex of step 2.2 agglomeration hole enlargement gained in the reactor, (proportionlity of vinylbenzene and methyl methacrylate is in the mixture: vinylbenzene 75% to add the mixture of grafted monomer vinylbenzene and auxiliary material monomers methyl methacrylate at twice, methyl methacrylate 25%), the proportionlity of the big particle diameter grafting trunk latex of agglomeration hole enlargement gained and the mixture of vinylbenzene and auxiliary material monomers methyl methacrylate is, the big particle diameter grafting trunk latex 60% of agglomeration hole enlargement gained, the mixture 40% of vinylbenzene and auxiliary material monomers methyl methacrylate, the mixture of vinylbenzene and auxiliary material monomers methyl methacrylate adds 0.8-1.2 hour pitch time twice, mixture=1 with big particle diameter grafting trunk latex+vinylbenzene and auxiliary material monomers methyl methacrylate, corresponding adding emulsifying agent of while, initiator, reductive agent, complexing agent, conditioning agent and medium, wherein emulsifying agent hydrogen peroxide second propyl benzene 2.25%, initiator ferrous sulfate 0.2%, reductive agent Diao Bai piece 0.07%, complexing agent EDTA0.06%, conditioning agent mercaptan 0.30%, 70 ℃ of constant temperature reacted 4-8 hour down, surveying transformation efficiency reaches 98% and cools off discharging when above, with calcium chloride solution cohesion, dehydration, washing, it is nuclear that drying makes with butyl polyacrylate rubber, hard monomer (mixture of vinylbenzene and auxiliary material monomers methyl methacrylate) is the plastic modifier white powder of shell.
Embodiment two
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
Cross-linking monomer is that Vinylstyrene, auxiliary material monomer are ethyl propenoate in the small particle size grafting trunk latex synthesis step, the proportionlity of butyl acrylate, Vinylstyrene and ethyl propenoate is a butyl acrylate 70%, Vinylstyrene 1%, ethyl propenoate 29%.
Embodiment three
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
Cross-linking monomer is a glycidyl methacrylate in the small particle size grafting trunk latex synthesis step, the auxiliary material monomer styrene.Butyl acrylate, glycidyl methacrylate and cinnamic proportionlity are butyl acrylate 80%, glycidyl methacrylate 5%, vinylbenzene 15%.
Embodiment four
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
α, beta-unsaturated carboxylic acid are methacrylic acid in the synthetic agglomerating latex step, and the proportionlity of butyl acrylate and methacrylic acid is a butyl acrylate 70%, methacrylic acid 30%.
Embodiment five
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
Butyl acrylate and acrylic acid proportionlity are butyl acrylate 80% in the synthetic agglomerating latex step, vinylformic acid 20%.
Embodiment six
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
The proportionlity of agglomerating latex and branch trunk latex is an agglomerating latex 0.5% in the agglomeration hole enlargement step, grafting trunk latex 99.5%.
Embodiment seven
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
The proportionlity of agglomerating latex and grafting trunk latex is an agglomerating latex 5% in the agglomeration hole enlargement step, big particle diameter grafting trunk latex 95%.
Embodiment eight
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
Auxiliary material monomer in the preparation graft polymerization step in the grafted monomer is a methyl methacrylate, and the proportionlity of vinylbenzene and methyl methacrylate is a vinylbenzene 50%, methyl methacrylate 50%.
Embodiment nine
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
There is not the auxiliary material monomer in the grafted monomer in the preparation graft polymerization step.
Embodiment ten
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
Big particle diameter grafting trunk latex and grafted monomer proportionlity through step 2.2 agglomeration hole enlargement gained in the graft polymerization step are: big particle diameter grafting trunk latex 20%, grafted monomer 80%.
Embodiment 11
With a kind of preparation method for modifier of poly n-butyl acrylate plastic of embodiment one, its difference is:
Big particle diameter grafting trunk latex and grafted monomer proportionlity through step 2.2 agglomeration hole enlargement gained in the graft polymerization step are: big particle diameter grafting trunk latex 70%, grafted monomer 30%.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (9)
1. preparation method for modifier of poly n-butyl acrylate plastic is characterized in that may further comprise the steps:
A, synthetic small particle size grafting trunk latex
Acrylate, cross-linking monomer and auxiliary material monomer are mixed, add corresponding emulsifying agent, initiator, conditioning agent and medium; Above each material is added in the reactor; Temperature is the 60-85 degree in the controlling reactor, reaction times 4-6 hour; Measure transformation efficiency and reach 95%, small particle size grafting trunk latex is made in discharging during PH=6.0;
B, the hole enlargement of grafting trunk latex particle
B1, synthetic agglomerating latex---acrylate is mixed with α, β unsaturated carboxylic acid, and add corresponding emulsifying agent, initiator, conditioning agent and medium, above each material is added reactor, temperature is the 60-85 degree in the controlling reactor, reaction times 4-6 hour, transformation efficiency reaches discharging in 98% o'clock, makes agglomerating latex;
B2, agglomeration hole enlargement---under 17-45 ℃ of temperature condition, agglomerating latex is added in the small particle size grafting trunk latex, stir, make it the agglomeration hole enlargement, make big particle diameter grafting trunk latex through the agglomeration hole enlargement;
C, graft polymerization
To add through the big particle diameter grafting trunk latex of agglomeration hole enlargement in the reactor, with grafted monomer vinylbenzene and the monomeric mixture of at least a auxiliary material, add at twice, make the micelle swelling, twice adds pitch time is 0.8-1.2 hour, in reactor, add corresponding required emulsifying agent, initiator, conditioning agent and medium simultaneously, 60-85 ℃ was reacted 4-8 hour down, and the cooling discharging is condensed with calcium chloride solution, dehydration, washing, drying make modifier of poly n-butyl acrylate plastic.
2. according to the described preparation method for modifier of poly n-butyl acrylate plastic of claim 1, it is characterized in that: the acrylate in the described steps A, cross-linking monomer and auxiliary material monomer compound percentages are acrylate 70-99.9%; Cross-linking monomer 0.1-10%; Auxiliary material monomer 0-30%.
3. according to the described preparation method for modifier of poly n-butyl acrylate plastic of claim 2, it is characterized in that: described cross-linking monomer is a kind of in Vinylstyrene, cyanuric acid alkatriene third fat, glycidyl methacrylate, O-phthalic base diallyl, the Ethylene glycol dimethacrylate.
4. according to the described preparation method for modifier of poly n-butyl acrylate plastic of claim 3, it is characterized in that: described auxiliary material monomer is a kind of in vinylbenzene, methyl methacrylate, the ethyl propenoate.
5, according to the described preparation method for modifier of poly n-butyl acrylate plastic of claim 2, it is characterized in that: the weight percent of acrylate among the described step B1 and α, β unsaturated carboxylic acid is acrylate 70-90%; α, beta-unsaturated carboxylic acid 10-30%, described α, beta-unsaturated carboxylic acid are methacrylic acid or vinylformic acid.
6, according to the described preparation method for modifier of poly n-butyl acrylate plastic of claim 5, it is characterized in that: agglomerating latex among the described step B2 and grafting trunk latex proportionlity are agglomerating latex 0.5-5%; Grafting trunk latex 95-99.5%.
7, according to the described preparation method for modifier of poly n-butyl acrylate plastic of claim 5, it is characterized in that: the monomeric proportionlity of vinylbenzene among the described step C and auxiliary material is vinylbenzene 50-100%; Auxiliary material monomer 0-50%.
8, according to the described preparation method for modifier of poly n-butyl acrylate plastic of claim 7, it is characterized in that: the auxiliary material monomer in the described graft polymerization is a kind of in vinyl cyanide, methyl methacrylate, glycidyl methacrylate, the amides monomer.
9, described according to Claim 8 preparation method for modifier of poly n-butyl acrylate plastic is characterized in that: the weight percent through the big particle diameter grafting trunk latex of agglomeration hole enlargement and grafted monomer among the described step C is the big particle diameter grafting trunk latex 20 to 90% through the agglomeration hole enlargement; Grafted monomer 10 to 80%.
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| CN 200510041581 CN1919888A (en) | 2005-08-23 | 2005-08-23 | Preparation method for modifier of poly n-butyl acrylate plastic |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890085A (en) * | 2012-04-03 | 2014-06-25 | Lg化学株式会社 | Composition containing cross-linked polymer nanoparticles, method for preparing copolymer using the composition, and vinyl chloride resin having enhanced foam moldability |
| CN104119628A (en) * | 2013-04-26 | 2014-10-29 | 彭朕财 | Transparent PMMA (polymethyl methacrylate) particle powder toughening agent |
| CN112210044A (en) * | 2020-10-29 | 2021-01-12 | 山东鼎鼎化学科技股份有限公司 | Weather-resistant impact-resistant modifier and preparation method and application thereof |
| CN113278117A (en) * | 2021-05-25 | 2021-08-20 | 四川兴彩高新材料有限公司 | ASA resin, ASA non-folding white film and preparation method thereof |
-
2005
- 2005-08-23 CN CN 200510041581 patent/CN1919888A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890085A (en) * | 2012-04-03 | 2014-06-25 | Lg化学株式会社 | Composition containing cross-linked polymer nanoparticles, method for preparing copolymer using the composition, and vinyl chloride resin having enhanced foam moldability |
| CN104119628A (en) * | 2013-04-26 | 2014-10-29 | 彭朕财 | Transparent PMMA (polymethyl methacrylate) particle powder toughening agent |
| CN104119628B (en) * | 2013-04-26 | 2017-06-16 | 彭朕财 | Transparent PMMA particle powders toughener |
| CN112210044A (en) * | 2020-10-29 | 2021-01-12 | 山东鼎鼎化学科技股份有限公司 | Weather-resistant impact-resistant modifier and preparation method and application thereof |
| CN113278117A (en) * | 2021-05-25 | 2021-08-20 | 四川兴彩高新材料有限公司 | ASA resin, ASA non-folding white film and preparation method thereof |
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