CN101421344A - Hybrid impact modifiers and method for preparing the same - Google Patents
Hybrid impact modifiers and method for preparing the same Download PDFInfo
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- CN101421344A CN101421344A CN200780013171.6A CN200780013171A CN101421344A CN 101421344 A CN101421344 A CN 101421344A CN 200780013171 A CN200780013171 A CN 200780013171A CN 101421344 A CN101421344 A CN 101421344A
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Abstract
The present invention relates to hybrid impact modifiers prepared by: either spray drying, coagulation, freeze coagulation or other known recovery methods of a mixture of a latex or slurry of standard impact modifiers and a slurry of a mineral filler, either simultaneous drying (by spray-drying, coagulation other known recovery possible methods) of (i) a latex or slurry of standard impact modifiers and of (ii) a slurry of a mineral filler, further to the coagulation or freeze coagulation, if any, there is a filtration and drying step to recover these hybrid impact modifiers as a powder. The host polymers to be impact modified, can be any thermoplastic. Advantageously it can be polyvinyl chloride (PVC), polyamide (PA), polymethyl methacrylate (PMMA), polystyrene (PS), polycarbonate (PC), thermoplastic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexanedimethanol terephthalate, and polyolefins such as polyethylene (PE), polypropylene (PP), and any other matrix polymer which can be improved by an impact modifier. The present invention also relates to the use of said hybrid impact modifiers in thermoplastic polymers. The present invention also relates to a thermoplastic polymer containing said hybrid impact modifiers. The present invention also relates to hybrid impact modifiers having improved powder properties (flowability, lumping/caking resistance, segregation between the organic and the mineral parts). The present invention also relates to a thermoplastic polymer containing said hybrid impact modifiers with better dispersion homogeneities.
Description
Technical field
The present invention relates to by spraying drying, condense, freeze or the hybrid impact modifiers (for example being used for PVC) of other known recovery method preparation.More particularly, the present invention relates to hybrid impact modifiers by being prepared as follows:
Reclaim the hybrid impact modifiers of these powder types, described powder is introduced treated in the impact-resistant modified thermoplastic matrix then.Described powder mix under molten state with this thermoplastic matrix or with the powder for drying blend of this thermoplastic matrix.Randomly, can introduce other additive simultaneously as hybrid modifier powder.
Background technology
Main by introducing the shock peening that the impact modified additive of polymkeric substance (for example methacrylate butadi ene styrene copolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS) or acrylic core/shell polymer (AIM) and CPE (chlorinatedpolyethylene)) obtains rigid polyvinyl chloride (PVC).Usually synthesize these properties-correcting agent by emulsion or suspension polymerization or under slurry form, HDPE is carried out chlorination with preparation CPE at aqueous phase.No matter for any impact modifying agent, before the impact modifying agent that reclaims (for example spraying drying, cohesion) powder type, polymer modifiers all is dispersed in the water (latex, suspension or slurry).
Often the mineral filler (for example silica or lime carbonate) of some primary particle diameters in micron or nanometer range added in the above-mentioned impact modifying agent, be mainly improve its powder properties (flowable, anti-agglomerating/anti-caking ...), but so that its batch feed.Under the sort of situation, during the removal process of impact modifying agent or afterwards, mineral filler is added in the powder of impact modifying agent with powder type.
United States Patent (USP) 4278576 relates to the separation and the improvement of impact modifying agent polymer powder, and relates to the blend of thermoplastic matrix polymers and such impact modifying agent polymer powder.Described separation method can be spraying drying, cohesion, grinding or other method.As described in United States Patent (USP) 4278576, after described impact modifying agent polymer formation but before it is separated with powder type or during, introduce median size and be about 0.04～1 micron the lime carbonate that is coated with stearate, with respect to impact modifying agent polymkeric substance and the lime carbonate that is coated with stearate, the amount of the lime carbonate of introducing that is coated with stearate is about 0.5～50 weight %, is preferably 0.5～25 weight %.That is to say that the lime carbonate that is coated with stearate adds during the polymerization technique that forms polymkeric substance, perhaps polymer formation after but adding before polymkeric substance separates with powder type.When separating, can add above 50% the lime carbonate that is coated with stearate and also partly remove the lime carbonate that is coated with stearate by method of sieving thereafter, so that its content in final product is reduced to below 50% with polishing.The most preferred lime carbonate that is coated with stearate is the product of being sold with trade mark Winnofil S by Imperial Chemical Industries at present, and its particle diameter is about 0.075 micron and do not assemble.Described " matrix " polymkeric substance can be that polyvinyl chloride, nylon, polymethylmethacrylate, polystyrene, thermoplastic polyester (for example polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid cyclohexanedimethanoester ester) and polyolefine (for example polyethylene, polypropylene) and any other can pass through the improved matrix polymer of impact modifying agent.According to the method for US4278576 isolating and for the impact modifying agent polymkeric substance of the part of composition be methacrylic ester-butadiene-styrene graftomer (MBS) (for example those described in the U.S. Patent No. 3985704), acrylic core/shell polymer (AIM) (for example those described in the U.S. Patent No. 3985703) or wherein rubber content can be the analogue of these polymkeric substance of 60～100% of total polymer material.
Example I～III of US4278576 has described use standard emulsion polymerization technology and has prepared acrylic core/shell polymer, in this preparation, used 79.2 parts butyl acrylate, 0.4 part the diacrylate butanediol ester and as 0.4 portion of diallyl maleate of rubber-like nuclear and subsequently as 20 parts of methyl methacrylates of subordinate phase.Carry out the spraying drying of emulsion in the presence of as the air of drying medium.For improving the flowing property of spraying drying and powder, in inlet air stream, add particulate additive (for example, being coated with the lime carbonate of stearate).
Unfortunately, such inorganics introducing route can not prevent some defective (for example heterogeneity and segregation (segregation) problem of dispersion and concentration).When the content with respect to organic impact modifying agent, the amount of mineral material is especially true on 2% or 3% the time.
The objective of the invention is to improve the homogeneity of dispersion and concentration and prevent segregation (particularly during transportation or feed bin transfer).
Being used for obtaining these improved methods is: at water-dispersion mixed polymer properties-correcting agent and mineral filler mutually, that is to say, the slurry of modifier dispersion (emulsion, suspension or slurry) with mineral filler mixed.Under the sort of situation, mineral parts not only can be a lime carbonate, can also be the inorganic materials of zeolite, hydrotalcite, clay, polynite, perlite and any other type of can slurry form obtaining.In case described organic/inorganic blend is full and uniform, just can carry out the standard recovery processes (spraying drying, condense, freeze or other known recovery method) of above-mentioned impact modifying agent.Another path can be simultaneously dry (by spraying drying, cohesion or other known possible recovery method) organic water dispersion and inorganic slurry, this means by two independent nozzles (or inlet) two kinds of different products based on water (being organic and the mineral product) are introduced in the dry chamber (or cohesion equipment) simultaneously.No matter be any method, described final product has been considered to hybrid impact modifiers, when original mineral partly is present in when being of a size of in the micron-sized primary granule, this hybrid impact modifiers is a composite modifier, perhaps, when mineral partly are present in when being of a size of in the nano level primary granule, this hybrid impact modifiers is a nano composite modifying agent.In fact, the powdered material of gained is present in the primary particle, and this primary particle contains the organic phase that closely mixes with mutually inorganic.
Summary of the invention
The present invention relates to hybrid impact modifiers by being prepared as follows:
If described cohesion arranged or freeze, then exist filter and drying step to reclaim the hybrid impact modifiers of these powder types.
Treat that impact-resistant modified main polymer can be any thermoplastic material.Advantageously, this thermoplastic material can be that polyvinyl chloride, polymeric amide, polymethylmethacrylate, polystyrene, polycarbonate, thermoplastic polyester (for example polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid cyclohexanedimethanoester ester) and polyolefine (for example polyethylene, polypropylene) and any other can pass through the improved polymkeric substance of impact modifying agent.Main polymer is polyvinyl chloride or polycarbonate advantageously.
The invention still further relates to the application of described hybrid impact modifiers in thermoplastic polymer.
The invention still further relates to the thermoplastic polymer that contains described hybrid impact modifiers.This thermoplastic polymer that contains described hybrid impact modifiers can be used as coating and is used for the manufacturing of section bar, pipe or wooden partition.
The invention still further relates to goods with above-mentioned thermoplastic compounds.These goods can be section bar, pipe or wooden partition.
The invention still further relates to powder properties with improvement (flowable, anti-agglomerating/anti-caking) hybrid modifier.Described final product has been considered to hybrid impact modifiers, when original mineral partly is present in when being of a size of in the micron-sized primary granule, this hybrid impact modifiers is a composite modifier, perhaps, when mineral partly are present in when being of a size of in the nano level primary granule, this hybrid impact modifiers is a nano composite modifying agent.In fact, the powdered material of gained is present in the primary particle, and this primary particle contains the organic phase that closely mixes with mutually inorganic.
The present invention has a lot of advantages:
Compare with following material, described hybrid modifier has the impact property of improvement: (i) product, (ii) independent organic modifiers and the (iii) independent mineral filler that is produced by the direct blend of two kinds of starting powders (organic modifiers and mineral filler).Therefore, when preparation hybrid modifier of the present invention, between organic moiety and inorganic part, there is the obvious synergistic effect.
After being incorporated into this hybrid impact modifiers in the thermoplastic matrix, by using conventional processing technology (for example extrude, injection-molded), with the two-phase (organic and inorganic) of hybrid impact modifiers all respectively with reduce to its separately the size dispersion of original primary particle diameter in the main body thermoplastic matrix.Yet because the high-compatibility of organic impact modifying agent and main body thermoplastic matrix is compared with the common way when directly with powder type mineral filler being introduced, this mineral filler can be dispersed in this matrix better.
The novel method of this preparation hybrid impact modifiers also can be thought by closely combining of mineral filler and organic impact modifying agent mineral filler to be introduced new mode in the plastic substrate, thereby be dispersed the standard mineral filler, this standard mineral filler both can be to have usually that special surface is handled and with the main body plastic substrate mineral filler of consistency is arranged, and also can be without any the surface-treated mineral filler.In other words, this impact modifying agent can be used as the expanding material of mineral filler and main polymer matrix.
Embodiment
For described standard impact modifiers, that can mention as an example has: ABS, MBS, AIM and CPE.Advantageously, impact modifying agent is the form with thin primary granule of elastomer core and at least one thermoplastic shell, and the size of primary granule is usually less than 1 micron and advantageously be 50～500 nanometers.Advantageously by the emulsion polymerization prepared impact modifying agent.The content of impact modifying agent in thermoplastic matrix is 0～25 weight %, is preferably 0～10 weight %.
For example, endorsing by following material of described impact modifying agent formed:
● isoprene or dienite; Or
● have the isoprene copolymer of the vinyl monomer of 30mol% at the most; Or
● have the butadienecopolymer of the vinyl monomer of 30mol% at the most.
Vinyl monomer can be vinylbenzene, ring-alkylated styrenes, vinyl cyanide or (methyl) alkyl acrylate.
Described nuclear also can be made up of following material:
(methyl) acrylic acid alkyl ester homopolymer; Or
Has (methyl) alkyl acrylate copolymer of the monomer of 30mol% (being selected from another (methyl) alkyl acrylate and vinyl monomer) at the most.
Advantageously, described (methyl) alkyl acrylate is a butyl acrylate.Vinyl monomer can be vinylbenzene, ring-alkylated styrenes, vinyl cyanide, divinyl or isoprene.
Advantageously, described endorse crosslinked wholly or in part.It is enough adding at least difunctionality or trifunctional monomer in the preparation process of this nuclear.These monomers can be polynary (methyl) acrylate (for example diacrylate butanediol ester, two (methyl) vinylformic acid fourth diester (butylene di (meth) acrylate), trimethylammonium vinylformic acid trishydroxymethyl propyl ester) that allyl methacrylate(AMA), diallyl maleate maybe can be selected from polyvalent alcohol.Other difunctional monomer for example can be Vinylstyrene, trivinylbenzene, vinyl acrylate and methacrylic vinyl acetate.Also unsaturated functional monomer (for example unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid and unsaturated epoxide) can be introduced in the nuclear, with the stone grafting branch or during polyreaction as comonomer, thereby carry out crosslinked to nuclear.That can mention as an example, has maleic anhydride, (methyl) vinylformic acid and a glycidyl methacrylate.Described shell is one of vinylbenzene, ring-alkylated styrenes, vinyl cyanide or imperplex or above-mentioned these monomers that contain 70mol% at least and at least a multipolymer that is selected from the comonomer of other above-mentioned monomer, another (methyl) alkyl acrylate, vinyl-acetic ester and vinyl cyanide.Unsaturated functional monomer (for example unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid and unsaturated epoxide) or other functional monomer can be introduced in the shell, with the shell joint branch or during polyreaction as comonomer, thereby carry out functionalized to shell.That can mention as an example, has: maleic anhydride, (methyl) vinylformic acid and glycidyl methacrylate, (methyl) Hydroxyethyl acrylate.
As the example of impact modifying agent, that can mention has the nuclear-shell copolymer with polystyrene homopolymer or shell copolymers and the nuclear-shell copolymer with PMMA homopolymer or shell copolymers.The nuclear-shell copolymer that has the bivalve in addition, wherein in this bivalve is made by polystyrene and another shell is outside made by PMMA.The example and the preparation method of impact modifying agent have been described: US4180494, US3808180, US4096202, US4260693, US3287443, US3657391, US4299928, US3985704 and US5773520 in following patent.
Advantageously, described nuclear accounts for the 65 weight %～99.5 weight % of impact modifying agent and 35 weight %～0.5 weight % that described shell accounts for impact modifying agent, and preferred described nuclear accounts for the 85 weight %～98 weight % of impact modifying agent and 15 weight %～2 weight % that described shell accounts for impact modifying agent.
Described impact modifying agent can be soft/gravity die.As the example of soft/hard type impact modifier, can mention the impact modifying agent of forming by following material:
(i) nuclear of the Vinylstyrene of the vinylbenzene of 75～80 parts the divinyl that comprises 93mol% at least, 5mol% and 0.5～1mol%, with
(ii) 25～20 parts the bivalve that has identical weight basically, wherein inner casing is made by polystyrene and another shell is made by PMMA homopolymer or multipolymer.
As another example of soft/hard type impact modifier, having of can mentioning has the soft/hard type impact modifier of poly-(butyl acrylate) or butyl acrylate/divinyl or poly-(2-ethylhexyl acrylate) or poly-(2-ethylhexyl acrylate)/divinyl cross-linking copolymer nuclear (85～98 parts) and PMMA homopolymer or shell copolymers (15～2 parts).
Described impact modifying agent can also be hard/soft/gravity die, that is to say that described impact modifying agent contains stone, soft shell and duricrust successively.This hard part can by above-mentioned soft/polymkeric substance of the shell of hard multipolymer forms, and this soft part can by above-mentioned soft/polymkeric substance of the nuclear of multipolymer is formed firmly.
For example, can mention hard/soft/hard type impact modifier of forming by following material:
(i) nuclear of making by the methyl methacrylate/ethyl acrylate multipolymer;
(ii) by butyl acrylate/styrol copolymer make the layer;
The (iii) shell of making by the methyl methacrylate/ethyl acrylate multipolymer.
Described impact modifying agent can also be hard (nuclear)/soft/semi-hard type.In this case, described " semihard " shell is made up of two shells, and one is that middle case and another are shells.This middle case is methyl methacrylate, vinylbenzene and at least a monomeric multipolymer that is selected from alkyl acrylate, divinyl and isoprene.This shell is PMMA homopolymer or multipolymer.
Firmly/example of soft/semi-hard type impact modifying agent is successively by the following impact modifying agent of forming:
(i) nuclear of making by the methyl methacrylate/ethyl acrylate multipolymer;
The (ii) shell of making by butyl acrylate/styrol copolymer;
The (iii) shell of making by methyl methacrylate/butyl acrylate/styrol copolymer; With
The (iv) shell of making by the methyl methacrylate/ethyl acrylate multipolymer.
For described mineral filler, according to the present invention, the Mohs' hardness of this mineral filler is less than 6 and for example be less than or equal to 4.Mohs' hardness causes being used to process the wearing and tearing of the instrument and the machine of the composition that contains described impact modifying agent greater than 6 mineral filler.
Measure by any method known to those skilled in the art, according to the particle diameter of mineral filler of the present invention less than 1 μ m.
Example according to mineral filler of the present invention can comprise: the inorganic materials of the PCC (NPCC) of the natural whiting of grinding (GCC), sedimentary lime carbonate (PCC), nanoscale, clay, polynite (nanometer-clay), zeolite, perlite or any other type of can slurry form obtaining.
Ratio for described standard impact modifiers and described mineral filler, preferred this mineral filler accounts for 0.1～95 weight %, more preferably 1～50 weight % and further preferably account for 3～20 weight % is with respect to the total amount of described standard impact modifiers and described mineral filler.
For the slurry of mineral filler, it is the water dispersion that solids content is preferably 5～80% and more preferably 25～60% mineral filler.This water dispersion can contain any specific tensio-active agent, dispersion agent, additive or the filling surface that can advantageously improve stock quality (stability, viscosity or with the consistency of main body matrix) to be handled.
The thermoplastic polymer that contains described hybrid impact modifiers also can contain other additive, for example other mineral filler, organic or inorganic pigment, carbon black, carbon nanotube, granulated glass sphere, glass fibre, fire retardant and/or toughener.
The thermoplastic polymer that contains described hybrid impact modifiers can be used as coating and the manufacturing that is used for section bar, pipe or wooden partition.
The invention still further relates to goods with above-mentioned thermoplastic compounds.These goods can be section bar, pipe or wooden partition.
Embodiment
Embodiment 1
Prepare hybrid impact modifiers with spraying drying
Prepare impact modifier latex according to U.S. Patent No. 4278576 described technology, the standard emulsion polymerization technology has been adopted in this preparation.That is, adopt 84.2 parts of butyl acrylates, 0.4 part of diacrylate butanediol ester and, carry out 15 parts Polymerization of Methyl subsequently as 0.4 part of diallyl maleate preparation nuclear/shell acrylic polymers of elastomer core.Solids content is 40%.
Prepare CaCO according to the described technology of Japanese Patent No.59057913
3Slurry.That is, by mixing 270 parts of water, 0.72 part of sodium polyacrylate and 729.3 parts of CaCO that diameter is 0.2～0.6.mu
3Stir 20min with 0.6% moisture and under shearing rate 5 * 102/s and obtain described slurry.
With following mixed latex and slurry: 9.11kg (9110 parts) latex and 8.9kg (8.9 parts) slurry, and under the condition that typically is used for latex separately this mixture of spraying drying.The powder diameter of gained is about 150.mu.
Characterize hybrid impact modifiers with microscopy, homogeneity and segregation test.
Microscopy:By scanning electronic microscope with backscattering pattern observation sample, to distinguish CaCO
3And acrylic particles.CaCO
3Show as white phase and acrylic acid or the like and partly show as grey form and aspect.In mixing particle, see CaCO as white point
3Particle (referring to Fig. 1 and Fig. 2).Since backscattering, CaCO
3Be white in color in the drawings, and be positioned at the inside of AIM miscellaneous granules.
Homogeneity:The CaCO that in 5 small samples of hybrid impact modifier powder, measures by fluoX
3Dosage.
We can observe the CaCO of sample
3Content have low-down deviation.
Segregation test:This test is made up of the fluidisation of sample, and checks CaCO in the powder that reclaims in the top and the bottom of fluidisation device
3Content whether identical.
CaCO in thin powder particle and big powder particle
3Content closely similar, do not observe segregation.
Embodiment 2
Impact modifier latex and CaCO
3Slurry is identical with embodiment 1.But,, respectively each suspension is carried out spraying drying with the condition identical with embodiment 1.
Acrylic acid or the like/CaCO with 85/15
3Than the powder that mixes gained.
Characterize this mixture with the condition identical with embodiment 1.
Microscopy:By scanning electronic microscope with backscattering pattern observation sample to distinguish CaCO
3And acrylic particles.CaCO
3Show as white phase and acrylic acid or the like and partly show as grey form and aspect.CaCO
3Particle is (referring to Fig. 3 and Fig. 4) around the acrylic acid or the like particle.
Homogeneity:The CaCO that in 5 small samples of hybrid impact modifier powder, measures by fluoX
3Dosage.
Powdered mixture (AIM+CaCO
3) inhomogeneous.Observe CaCO
3The deviation of content very high (deviation is 2.7, and this deviation is 4 times of the deviation (0.65) that mixes the AIM/ slurry).
Segregation test:This test is made up of the fluidisation of sample, and checks CaCO in the powder that reclaims in the top and the bottom of fluidisation device
3Content whether identical.
At the segregation test period, for macrobead, the CaCO in the powder
3Content (12.6%) becomes and is lower than the CaCO of original mixture
3Content (14%), and the CaCO in the fine fraction
3Content (18.2%) is higher than the CaCO of original mixture
3Content (14%).Even so not harsh segregation test has also demonstrated significant segregation.
Claims (13)
1. the hybrid impact modifiers by being prepared as follows:
To the latex of (i) standard impact modifiers or slurry and (ii) the slurry of mineral filler carry out drying (handling) simultaneously by spraying drying, cohesion or other known possible recovery method,
If described cohesion arranged or freeze, then exist filter and drying step to reclaim the hybrid impact modifiers of these powder types.
2. the hybrid impact modifiers of claim 1, the Mohs' hardness of wherein said mineral filler is less than 6 and preferably be less than or equal to 4.
3. claim 1 or 2 hybrid impact modifiers, wherein said mineral filler are the inorganic materials of the PCC (NPCC), clay, polynite (nanometer-clay), zeolite, perlite of the natural whiting (GCC) that grinds, sedimentary lime carbonate (PCC), nanoscale or any other type that can obtain with slurry form.
4. according to each hybrid impact modifiers in the aforementioned claim, the ratio that wherein said mineral filler accounts for the total amount of described standard impact modifiers and described mineral filler is 0.1～95 weight %.
5. according to each hybrid impact modifiers in the aforementioned claim, the ratio that wherein said mineral filler accounts for the total amount of described standard impact modifiers and described mineral filler is 1～50%.
6. according to each hybrid impact modifiers in the aforementioned claim, the ratio that wherein said mineral filler accounts for the total amount of described standard impact modifiers and described mineral filler is 3～20%.
7. according to each hybrid impact modifiers in the aforementioned claim, wherein standard impact modifiers is selected from methacrylate butadi ene styrene copolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylic core/shell polymer (AIM) and CPE (chlorinatedpolyethylene).
8. according to each the application of hybrid impact modifiers in thermoplastic polymer in the aforementioned claim.
9. the application of claim 8, wherein said thermoplastic polymer is selected from polyvinyl chloride; Polymeric amide; Polymethylmethacrylate; Polystyrene; Polycarbonate; Thermoplastic polyester, for example polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid cyclohexanedimethanoester ester; And polyolefine, for example polyethylene, polypropylene.
10. the application of claim 8, wherein said thermoplastic polymer are polyvinyl chloride or polycarbonate.
11. contain the thermoplastic polymer of each hybrid impact modifiers among the claim 1-7.
12. containing, the thermoplastic polymer of claim 11, wherein said thermoplastic polymer be selected from following additive: other mineral filler, organic or inorganic pigment, carbon black, carbon nanotube, granulated glass sphere, glass fibre, fire retardant and/or toughener.
13. one kind comprises the described goods that contain the thermoplastic polymer of each hybrid impact modifiers among the claim 1-7, wherein said goods are pipe or section bar or wooden partition.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06290251 | 2006-02-14 | ||
| EP06290251.5 | 2006-02-14 | ||
| US78198006P | 2006-03-14 | 2006-03-14 | |
| US60/781,980 | 2006-03-14 | ||
| PCT/EP2007/051295 WO2007093565A1 (en) | 2006-02-14 | 2007-02-09 | Hybrid impact modifiers and method for preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101421344A true CN101421344A (en) | 2009-04-29 |
| CN101421344B CN101421344B (en) | 2014-12-17 |
Family
ID=37501644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780013171.6A Active CN101421344B (en) | 2006-02-14 | 2007-02-09 | Hybrid impact modifiers and method for preparing the same |
Country Status (6)
| Country | Link |
|---|---|
| CN (1) | CN101421344B (en) |
| BR (1) | BRPI0707815A2 (en) |
| GE (1) | GEP20115292B (en) |
| NZ (1) | NZ570563A (en) |
| SI (1) | SI1984442T1 (en) |
| UA (1) | UA90050C2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476900A (en) * | 2016-06-07 | 2019-03-15 | 阿肯马法国公司 | Polymer composition, preparation method, its purposes and the composition comprising it |
| CN111148813A (en) * | 2017-09-27 | 2020-05-12 | 阿科玛股份有限公司 | One-part polymer modifier |
| CN113862827A (en) * | 2021-09-06 | 2021-12-31 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Parallel composite elastic fiber, preparation method and application thereof, and composite spinning pack |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3985704A (en) * | 1975-06-19 | 1976-10-12 | Rohm And Haas Company | Methacrylate-butadiene-styrene graft polymers and process for their production |
| US4278576A (en) * | 1978-12-05 | 1981-07-14 | Rohm And Haas Company | Isolation and improvement of impact modifier polymer powders |
| JPH07100761B2 (en) * | 1986-10-09 | 1995-11-01 | 呉羽化学工業株式会社 | Polyarylene thioether composition |
| CN1412232A (en) * | 2001-10-12 | 2003-04-23 | 中国石油天然气股份有限公司 | Preparation method of impact modifier acrylate resin (ACR-II) for PVC |
-
2007
- 2007-02-09 UA UAA200811105A patent/UA90050C2/en unknown
- 2007-02-09 GE GEAP2007010897 patent/GEP20115292B/en unknown
- 2007-02-09 CN CN200780013171.6A patent/CN101421344B/en active Active
- 2007-02-09 NZ NZ570563A patent/NZ570563A/en not_active IP Right Cessation
- 2007-02-09 SI SI200730270T patent/SI1984442T1/en unknown
- 2007-02-09 BR BRPI0707815-3A patent/BRPI0707815A2/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476900A (en) * | 2016-06-07 | 2019-03-15 | 阿肯马法国公司 | Polymer composition, preparation method, its purposes and the composition comprising it |
| CN109476900B (en) * | 2016-06-07 | 2022-04-05 | 阿肯马法国公司 | Polymer composition, method for the production thereof, use thereof and composition comprising the same |
| CN111148813A (en) * | 2017-09-27 | 2020-05-12 | 阿科玛股份有限公司 | One-part polymer modifier |
| CN111148813B (en) * | 2017-09-27 | 2024-03-22 | 阿科玛股份有限公司 | One-part polymer modifier |
| CN113862827A (en) * | 2021-09-06 | 2021-12-31 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Parallel composite elastic fiber, preparation method and application thereof, and composite spinning pack |
| CN113862827B (en) * | 2021-09-06 | 2024-03-15 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Parallel composite elastic fiber, preparation method and application thereof, and composite spinning assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| GEP20115292B (en) | 2011-09-26 |
| BRPI0707815A2 (en) | 2011-05-10 |
| CN101421344B (en) | 2014-12-17 |
| SI1984442T1 (en) | 2010-08-31 |
| UA90050C2 (en) | 2010-03-25 |
| NZ570563A (en) | 2011-11-25 |
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