GB2128623A - Process for the coagulation of a polymer latex - Google Patents
Process for the coagulation of a polymer latex Download PDFInfo
- Publication number
- GB2128623A GB2128623A GB08323008A GB8323008A GB2128623A GB 2128623 A GB2128623 A GB 2128623A GB 08323008 A GB08323008 A GB 08323008A GB 8323008 A GB8323008 A GB 8323008A GB 2128623 A GB2128623 A GB 2128623A
- Authority
- GB
- United Kingdom
- Prior art keywords
- latex
- water
- rubber
- grafted
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920000126 latex Polymers 0.000 title claims abstract description 55
- 239000004816 latex Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 title claims abstract description 21
- 230000015271 coagulation Effects 0.000 title description 8
- 238000005345 coagulation Methods 0.000 title description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 20
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 16
- 230000008014 freezing Effects 0.000 claims abstract description 8
- 238000007710 freezing Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000010257 thawing Methods 0.000 claims abstract description 7
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- 229920006173 natural rubber latex Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000009757 thermoplastic moulding Methods 0.000 description 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Polymer latices are coagulated and dewatered by a process comprising: (a) freezing said latex to coagulate the polymer particles therefrom; (b) thawing the resulting coagulum and free water; and (c) separating the free water from the coagulum. The process is particularly suited to latices of grafted polybutadiene.
Description
SPECIFICATION
Process for the coagulation of a polymer latex
The present invention relates to a process for dewatering and coagulating a polymer latex by freezing the latex, thawing it, and separating the free water from the coagulation. The present invention is particularly useful in the preparation of thermoplastic molding compositions from grafted polybutadiene rubber blended with resinous polymers, methyl methacrylate, styrene, acrylonitrile or ethyl acrylate, and, more particularly, to the process for the preparation of the compositions whereby the grafted polybutadiene rubber latex is coagulated by freezing before being blended with the resinous polymers.
It has been known to prepare thermoplastic molding compositions from various resinous polymers and grafted rubber. These compositions have been prepared by blending the resinous polymers with the grafted rubber or by polymerizing the monmers used to prepare the polymers in the presence of the rubber. Schmitt et al, U.S. Patent 3,354,238 and DeLeone et al, U.S.
Patent 4,085,1 66, the disclosures of which are incorporated herein by reference, describe molding compositions wherein the resinous phase, comprised of terpolymers of methyl methacrylate, styrene and acrylonitrile or ethyl acrylate, and the rubber phase, comprised of polybutadiene grafted with methyl methacrylate and styrene, are blended together to provide compositions exhibiting improved clarity, heat distortion temperature, impact strength, color and gloss.
Previously, the grafted polybutadiene rubber latex used in preparing the blends has been coagulated by the use of ammonium acetate and the water removed therefrom by centrifuging.
This dewatered latex was then blended with a hydrocarbon solution (e.g. a toluene solution) of the resinous polymer to form the thermoplastic
resin rubber blend. The blending has been most conveniently accomplished using a devolatilizerextruder, described by Schmitt et al. In the devolatilizer-extruder, the two components of the blend, i.e. the resinous polymer solution and the grafted polybutadiene, are mixed, compounded, devolatilized and extruded in a short period of time. The term "devolatilization" refers to the step in which the nonpolymeric materials (toluene and water) are removed from the mixture. The devolatilizer-extruder is limited by the ability of the extruder to put in sufficient mechanical/thermal energy to evaporate the water and toluene from the dough.Since water has a very high latent heat of vaporization (more than six times that for toluene on a weight basis) throughput capacity of the devolatilizer-extruder would be greatly increased if the water in the grafted polybutadiene could be removed or significantly reduced prior to the blending operation. This would improve the throughput capacity of the devolatilizer-extruder almost in proportion to the reduction in the heat load.
The present invention is based on the discovery that grafted polybutadiene latex is readily coagulated and essentially completely dewatered by freezing the latex, for example at a temperature of about -200C to -250C, allowing the frozen latex to thaw to room temperature, and then removing the water therefrom, by centrifuging or other methods.
It is found that when the frozen latex thaws to room temperature, it spontaneously fractures into a mass of small (about 1 mm3) transparent particles from which 80 to 100% of the water is readily removed by centrifuging for a brief period of time. Any remaining water may be essentially completely removed from the grafted rubber by drying in air.
When the process of the invention is compared with prior methods of coagulation and dewatering, i.e. when the latex is coagulated with ammonium acetate and the resulting coagulated latex is centrifuged, it is found that only 5560% of the water is removed after relatively long centrifuging.
More generally, the present invention provides a process for coagulating and dewatering a polymer latex comprising: (a) freezing said latex to coagulate the polymer particles of said latex; (b) thawing the resulting coagulation and free water; and (c) separating the free water from the coagulation.
The improved process of the invention is particularly useful in the preparation of polymerrubber blends. It provides distinct advantages over prior methods of preparing the polymerrubber blends in that ammonium acetate is eliminated as a coagulant, thereby reducing corrosion of the devolatilizer-extruder; blending of the two phases is simplified because the compatibility of an all organic mixture is better than an organic-water mixture; the evaporation load of the devolatilizer-extruder is reduced by 7580%, depending on the prior removal of 90 to 100% of the water from the latex by freeze coagulation; and, the throughput capacity of the extruder is increased by at least 30 to 50%.
Although the improved method of the present invention is described herein with particular reference to the coagulation and de-watering of grafted polybutadiene latex, it will be understood that the method is applicable to other rubber latices, such as natural rubber latex, butadienestyrene latex, butadiene-acrylonitrile latex, and the like, and also to latices obtained by the emulsion polymerization of the resinous polymers, such as, for example, the resinous methylmethacrylate, styrene, acrylonitrile or ethyl acrylate terpolymer described by the aforementioned Schmitt et al and DeLeon et al patents.
There may be added to the rubber, either during or after formation, such addivites as heat and light stabilizers, antioxidants, lubricants, plasticizers, pigments, fillers and the like.
The resinous polymer and the rubber polymer may be blended together in any known way, such as by ball milling, hot roll milling, or the like; however, the preferred method of blending is by use of the aforementioned devolatilizer-extruder, wherein a solution of the resinous polymer and the freeze coagulated and de-watered rubber latex, in proportions to produce the desired compositions, are metered and mixed, compounded, devolatilized and extruded in a very short period of time. In the devolatilizer-extruder, the mixture is worked in a chamber under heat and vacuum so that new surfaces of the polymer mixture are continuously and rapidly exposed to vacuum to remove the solvent and remaining water before extruding the product.
The process of the invention, when applied to the blending operation using a devolatilizerextruder, reduces the heat input of the devolatilizer-extruder and increases the throughput significantly. For example, when a blend is prepared at a rate of 1000 pounds/hour using a toluene solution of the terpolymer resin and a grafted polybutadiene latex coagulated and de-watered by prior art methods, the evaporation load is 347 pounds/hour of toluene and 1 90 pounds/hour of water, representing a heat input of 246,214 BUT's/hour. If the grafted polybutadiene latex is freeze coagulated and dewatered according to the present invention, the evaporatoin load is 347 pounds/hour of toluene and 1 9 pounds/hour of water, representing a heat input of only 3273 BTU's/hour. An increase in throughput resulting therefrom will be at least 2550%.
The method of the present invention may be practiced in any convenient way. Thus, the latex may be frozen, thawed and de-watered by a variety of means. For example, the polybutadiene latex described herein may be grafted in a grafting reactor containing a heat exchanger in the form of coils or a number of tubes through which a refrigerant will be circulated to freeze the resulting latex. By changing from a refrigerant to heated water, the frozen latex will be thawed and discharged into a centrifuge where the water will be removed. The de-watered centrifuge cake may then be transferred via a suitable conveyor to a storage vessel from which it may be metered to the devolatilizer-extruder. However, the process of the invention is not limited to any particular means of freezing the latex, nor to any particular method of thawing it.De-watering may be accomplished by means other than centrifuging, such as by continuous filtration, or the like.
The following non-limiting examples further illustrate the invention.
Example 1
Polybutadiene rubber latex containing 75 parts of polybutadiene is blended with 20 parts of methyl methacrylate and 5 parts of styrene. The rubber-monomer ratio is 3:1. The monomers are then grafted onto the polybutadiene by a redox initiated polymerization using, based on
monomer, 0.05 part of t.butyl hydroperoxide, 0.6
part of sodium formaldehyde sulfoxylate,27 ppm, of ferric chloride .6 H20, and 127 ppm of ethylene diamine tetraacetic acid 0.4 sodium salt, at room temperature for 5-10 hours. To the latex is then added 0.3% (based on total latex) of 2,2'-methylenebis(2-t.butyl-4-ethylphenol) dissolved in 6 times its weight of toluene. The latex is then placed in a freezer at -20 two 2500 overnight.It is then removed and allowed to thaw to room temperature. On thawing, the latex fractures spontaneously into transparent particles which are then centrifuged for about 1 minute.
Following centrifuging, which removes 8090% of the water, the latex is air dried at room temperature. The dried particles contain < 1% water.
Example 2
Following the procedure of Example 2 of U.S.
4,085,166, a resinous terpolymer is prepared in toluene solution from a monomer mixture comprising 73 parts of methyl methacrylate, 22 parts of styrene and 5 parts of ethyl acrylate.
Example 3
Twenty parts of the freeze coagulated grafted polybutadiene latex of Example 1 is blended with 80 parts of the resinous terpolymer solution of
Example 2 to provide a final polybutadiene content of 14.5%. The blending is conducted using a devolatilizer-extruder at a temperature of about 250"F on the inlet end and about 6000F on the die end of the extruder under a vacuum of 25-27 inches of mercury.
The resulting transparent composition is then formed into various test specimens and tested.
Results are given below:
Notched Izod, fppi 1.7
Transparency, % 84
Haze, total (1) 11.2
12.8 Gloss, (2)
20% 53
60% 81
(1)
(2) measured through 1/8" molded specimens;
gloss values are obtained by measuring the
reflected light at the same angle (200, 600) as the
incident light.
The data obtained are comparable to those
obtained under the conditions described in the
Schmitt et al and DeLeone et al patents.
Example 4
A polybutadiene graft latex (rubber:monomer
ratio of 3:1) prepared as in Example 1 is blended
with the terpolymer composition of Example 2,
prepared by an emulsion polymerization method,
and the blended latices are frozen at -250C overnight. On thawing to room temperature, the
thawed mixture exhibits the same behaviour as
the grafted polybutadiene latex of Example 1.
Example 5
A natural rubber latex is frozen at a temperature of -20 OC to -25 OC in a freezer. The frozen latex is then allowed to thaw to room temperature and the rubber particles are then centrifuged to remove the water therefrom. More than 90% of the water is removed.
Similar results are obtained when a butadienestyrene rubber latex is used instead of natural rubber latex.
Claims (6)
1. A process for coagulating and dewatering a polymer latex comprising:
(a) freezing said latex to coagulate the polymer
particles of said latex;
(b) thawing the resulting coagulum and free
water; and
(c) separating the free water from the
coagulum.
2. A process according to Claim 1 wherein said water is removed by centrifugation.
3. A process according to Claim 1 wherein said polymer latex is rubber latex.
4. A process according to Claim 3 wherein said rubber latex is a grafted rubber latex.
5. A process according to Claim 3 wherein said grafted rubber latex is a grafted polybutadiene latex.
6. A process according to Claim 5 wherein said latex is coagulated by freezing to a temperature of at least -200C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42990582A | 1982-09-30 | 1982-09-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8323008D0 GB8323008D0 (en) | 1983-09-28 |
| GB2128623A true GB2128623A (en) | 1984-05-02 |
Family
ID=23705199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08323008A Withdrawn GB2128623A (en) | 1982-09-30 | 1983-08-26 | Process for the coagulation of a polymer latex |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE3334306A1 (en) |
| FR (1) | FR2533930A1 (en) |
| GB (1) | GB2128623A (en) |
| IT (1) | IT1174780B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021233750A1 (en) | 2020-05-19 | 2021-11-25 | Covestro Deutschland Ag | Method of manufacturing colorant-filled polyurethane particles |
| WO2021233749A1 (en) | 2020-05-19 | 2021-11-25 | Covestro Deutschland Ag | Method of manufacturing filled polyurethane particles |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB841758A (en) * | 1958-01-10 | 1960-07-20 | Us Rubber Co | Improvements in increasing the particle size of synthetic rubber latices |
| GB939482A (en) * | 1961-05-02 | 1963-10-16 | Goodrich Co B F | Improvements in and relating to agglomeration |
| GB1027150A (en) * | 1963-10-24 | 1966-04-27 | British Geon Ltd | Recovery of polymers |
| GB1064775A (en) * | 1963-08-02 | 1967-04-12 | Du Pont | Improvements in or relating to the isolation of elastomers |
| GB1102342A (en) * | 1963-07-22 | 1968-02-07 | Bonded Fibre Fab | Improvements in or relating to the production of elongated binder particles of polymeric materials |
| US3981854A (en) * | 1975-06-02 | 1976-09-21 | E. I. Du Pont De Nemours & Company | Chloroprene polymer isolation |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB304207A (en) * | 1928-01-16 | 1930-04-15 | Ig Farbenindustrie Ag | Improvements in or relating to the manufacture of artificial rubber |
| FR667256A (en) * | 1928-01-16 | 1929-10-15 | Ig Farbenindustrie Ag | Method for coagulating latex-like emulsions |
| DE3230128A1 (en) * | 1982-08-13 | 1984-02-16 | Bayer Ag, 5090 Leverkusen | FREEZER COAGULATION OF POLYMER DISPERSIONS |
-
1983
- 1983-08-26 GB GB08323008A patent/GB2128623A/en not_active Withdrawn
- 1983-09-22 DE DE19833334306 patent/DE3334306A1/en not_active Withdrawn
- 1983-09-26 FR FR8315259A patent/FR2533930A1/en active Pending
- 1983-09-27 IT IT49045/83A patent/IT1174780B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB841758A (en) * | 1958-01-10 | 1960-07-20 | Us Rubber Co | Improvements in increasing the particle size of synthetic rubber latices |
| GB939482A (en) * | 1961-05-02 | 1963-10-16 | Goodrich Co B F | Improvements in and relating to agglomeration |
| GB1102342A (en) * | 1963-07-22 | 1968-02-07 | Bonded Fibre Fab | Improvements in or relating to the production of elongated binder particles of polymeric materials |
| GB1064775A (en) * | 1963-08-02 | 1967-04-12 | Du Pont | Improvements in or relating to the isolation of elastomers |
| GB1027150A (en) * | 1963-10-24 | 1966-04-27 | British Geon Ltd | Recovery of polymers |
| US3981854A (en) * | 1975-06-02 | 1976-09-21 | E. I. Du Pont De Nemours & Company | Chloroprene polymer isolation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021233750A1 (en) | 2020-05-19 | 2021-11-25 | Covestro Deutschland Ag | Method of manufacturing colorant-filled polyurethane particles |
| WO2021233749A1 (en) | 2020-05-19 | 2021-11-25 | Covestro Deutschland Ag | Method of manufacturing filled polyurethane particles |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8323008D0 (en) | 1983-09-28 |
| FR2533930A1 (en) | 1984-04-06 |
| DE3334306A1 (en) | 1984-04-05 |
| IT1174780B (en) | 1987-07-01 |
| IT8349045A0 (en) | 1983-09-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |