WO1995009202A1 - Additives to improve surface characteristics of unsaturated polyester molding composition - Google Patents
Additives to improve surface characteristics of unsaturated polyester molding composition Download PDFInfo
- Publication number
- WO1995009202A1 WO1995009202A1 PCT/US1994/010962 US9410962W WO9509202A1 WO 1995009202 A1 WO1995009202 A1 WO 1995009202A1 US 9410962 W US9410962 W US 9410962W WO 9509202 A1 WO9509202 A1 WO 9509202A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thermosetting resin
- containing composition
- unsaturated polyester
- unsaturated
- moldable thermosetting
- 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.)
- Ceased
Links
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
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
Definitions
- the invention comprises an improved sheet molding composition that includes a resinous system comprising: (a) an unsaturated polyester comprising a poly condensation product of one or more dihydric or poly-hydric alcohols and one or more ethylenically unsaturated polycarboxylic acids and one or more saturated
- polyurethanes prepared from polyisocyanates, preferably diisocyanates,
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Low-profile resin compositions having improved surface smoothness which are useful for compression or injection molding or injection-compression molding into useful articles. In one aspect, the invention comprises an improved sheet molding composition that includes a resinous system comprising: (a) an unsaturated polyester comprising a poly condensation product of one or more dihydric or poly-hydric alcohols and one or more enthylenically unsaturated polycarboxylic acids and one or more saturated polycarboxylic acid; (b) one or more low-profile additives comprising thermoplastic polymers; (c) one or more olefinically unsaturated monomers which copolymerize with the unsaturated polyester; (d) one or more additives having both aliphatically unsaturated bonds and epoxy-functional groups or polar function groups. In addition, the system is completed by adding a catalyst, a filler, fiberglass and a mold release. The resinous system imparts improved surface smoothness and higher surface energies wich cause improved adhesion to surface coating.
Description
ADDITIVES TO IMPROVE SURFACE CHARACTERISTICS OF UNSATURATED POLYESTER MOLDING COMPOSITION
BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
The present invention relates to unsaturated polyester resin
compositions and more specifically to such compositions which feature a
smooth high energy finish characteristic.
DESCRIPTION OF THE RELATED ART Unsaturated polyester resin compositions are finding increased use in the automotive industry as sheet molding compound (SMC) formulations from which component parts especially body panels can be molded. The SMC polymer matrix resin compositions contain, in addition to the unsaturated polyesters and monomer components, so-called "low-profile" additive components which are polymers that act to prevent or reduce undesirable shrinkage as the composition is being molded into a thermoset article. Low-profile additives are added to unsaturated polyester resin compositions in order to obtain a composition which can be used in a sheet molding formulation and molded into thermoset articles. The surfaces of the molded articles truly reflect the surface characteristics of the mold.
In addition to unsaturated polyester resins, the sheet molding
compound formulations typically contain other ingredients including, for example, chemical thickeners. In such formulations, a chemical thickener
such as an alkaline material (for example, magnesium oxide or magnesium
hydroxide) is added to an uncured polyester along with fillers, glass fiber, and other standard materials. The thickener interacts with the system to increase the viscosity of the composition. This process is referred to as maturation and usually takes several days. After the maturation process is
complete, the thickened formulations are handlable and can easily be
placed into compression molds either by hand or by machine. Although the use of low-profile additives and thickening agents, as described, do effect some degree of improvement in the antishrinkage and surface smoothness characteristics of the unsaturated polyester
compositions, it is still not possible to achieve the degree of surface smoothness required of today's thermoset molded articles. Improved surface smoothness has been achieved through use of new low profile additives or by use of higher amounts of low profile additives, often impairing substrate adhesion to surface coatings.
SUMMARY OF THE PRESENT INVENTION
The present invention provides low-profile resin compositions having
improved surface smoothness which are useful for compression or injection molding or injection-compression molding into useful articles. In one aspect, the invention comprises an improved sheet molding composition that includes a resinous system comprising:
(a) an unsaturated polyester comprising a poly condensation product of one or more dihydric or poly-hydric alcohols and one or more ethylenically unsaturated polycarboxylic acids and one or more saturated
polycarboxylic acid; (b) one or more low-profile additives comprising thermoplastic
polymers;
(c) one or more olefinically unsaturated monomers which copolymerize with the unsaturated polyester;
(d) one or more additives having both aliphatically unsaturated
bonds and epoxy-functional groups or polar functional groups. In addition, the system is completed by adding a catalyst, a filler, fiberglass and a mold release.
The resinous system imparts improved surface smoothness and higher surface energies which cause improved adhesion to surface coating.
These and other aspects of the present invention will become more readily apparent by reference to the following detailed description of the embodiments as shown in the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention relates to the discovery of the use in a low- profile system of components and additives having both aliphatically unsaturated bonds and epoxy functional groups or polar groups which
remain compatible with a curing unsaturated polyester resin and monomer. When these compatible components are included in combination with low-
profile additives and used in sheet molding compositions, articles with very
smooth surfaces and good adhesion to surface coatings may be molded.
The unsaturated polyester component of the resinous system comprises the polycondensation reaction product of one or more dihydric
alcohols and one or more ethylenically unsaturated polycarboxylic acids.
Polycarboxylic acid includes polycarboxylic or dicarboxylic acids or anhydrides, polycarboxylic or dicarboxylic acid halides, and polycarboxylic or dicarboxylic esters. Suitable unsaturated polycarboxylic acids, and the corresponding anhydrides and acid halides that contain polymerizable carbon-to-carbon double bonds may include maleic anhydride, maleic acid, and fumaric acid. A minor proportion of the unsaturated acid, up to about forty mole percent, may be replaced by dicarboxylic or polycarboxylic acid that does not contain a polymerizable carbon-to-carbon bond. Examples of which include orthophthalic, isophthalic, terephthalic, succinic, adipic,
sebacic, methyl-succinic, and the like. Dihydric alcohols that are useful in preparing the polyesters include 1 ,2-propane diol (hereinafter referred to as
propylene glycol), dipropylene glycol, diethylene glycol, 1 ,3-butanediol, ethylene glycol, glycerol, and the like. Examples of suitable unsaturated polyesters are the polycondensation products of (1 ) propylene glycol and maleic and/or fumaric acids; (2) 1 ,3-butanediol and maleic and/or fumaric acids; (3-combinations of ethylene and propylene glycols (approximately 50 mole percent of less of ethylene glycol) and maleic and/or fumaric acid;
(4) propylene glycol, maleic and/or fumaric acids and dicyclopentadiene reacted with water. These examples are intended to be illustrative of suitable polyesters and are not intended to be all-inclusive. The acid number to which the polymerizable unsaturated polyesters are condensed
is not particularly critical with respect to the ability of the low-profile resin to be cured to the desired product. Polyesters which have been condensed to acid numbers of less than 100 are generally useful, but acid numbers less than 70 are preferred. The molecular weight of the
polymerizable unsaturated polyester may vary over a considerable range,
but ordinarily those polyesters useful in the practice of the present invention have a molecular weight ranging from 300 to 5000, and more preferably, from about 500 to 5000.
In preferred embodiments, the unsaturated polyester is present in amounts ranging from about 20 to 45 percent, by weight. Especially preferred concentrations of the unsaturated polyester are in the 28 to 35 percent, by weight, range.
Low-profile additives are materials that when mixed in an unsaturated polyester and cured, result in a multi-phase system. If the low-profile additive and the unsaturated polyester are compatible (from the standpoint that a gross phase separation does not take place) before cure, the system is known as a one-pack. Those mixtures which tend to separate into two or more layers on standing are known as a two-pack
resin system. This does, however, necessitate mixing immediately before use. Some polymers that are useful as low-profile additives include
homopolymers and copolymers of acrylic and methacrylic acid esters; cellulose acetate butyrate; vinyl acetate homopolymers and copolymers;
polyurethanes prepared from polyisocyanates, preferably diisocyanates,
and polyols; numerous saturated polyesters; polycaprolactone; styrenebutadiene copolymers, some modified celluloses, and certain alkyl oxide polymers. The low profile additives may also include hydroxyl
terminated polyethers. These polyethers are based on propylene oxide, or block copolymers in which one of the blocks consist of propylene oxide.
The above list of low-profile additives is not intended to list all low-profile additives but rather to show examples of materials which have been used to cause the multiphase morphology present in low profile resins. In preferred embodiments the thermoplastic additive is present in amounts ranging from 5 to 30 percent, by weight, based on the total four component resinous system. Especially preferred concentrations of thermoplastic additive are in the 7 to 20 percent, by weight range.
The monomer component of the resinous system comprises materials that copolymerize with the unsaturated polyester. The olefinically unsaturated monomer that is copolymerizible with the unsaturated polyester is most generally styrene, however, methyl-styrene is also useful. In preferred embodiments the monomer is present in amounts ranging from 25 to 65 percent, by weight. Especially preferred concentrations of monomer are in the 35 to 50 percent, by weight range.
The additive component of the resinous system comprises materials having aliphatically unsaturated bonds and polar functional groups known to promote adhesion,- including but not limited to expoxy, amides, diazols, triazols, amines and acids. The additive is preferably vermonia oil, vernolic acid esters, partially epoxidized vegetable oils such as soybean oil and linseed oil, partially epoxidized soybean and linseed fatty acid esters, glycidyl methacrylate, glycidyl acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate and tetrabromo bisphenol A diacrylate and the like.
The resinous system of this invention is suitable for mixing with other ingredients in order to form a sheet molding composition. For example, the resinous system is suitable for mixing with chemical thickeners which are physically mixed into the resin emulsion. The chemical thickeners generally include metal oxides, hydroxides and alkoxides of Group II, III or IV from the Periodic Table. Calcium oxide and magnesium oxide or the respective hydroxides are most often employed. In preferred embodiments, the thickener is present in amounts ranging from about 0.5 to about 6 parts, by weight. The thickener is generally suspended in a carrier resin, as is known in the art. In preferred embodiments the carrier material comprises a composition which does not react with the thickener such as for example, polymethylmethacrylate, polyvinylacetate, saturated or unsaturated polyesters, and similar materials well-known in the art. In preferred embodiments the carrier resin is present in amounts ranging from about 0.5 to about 8 parts, by weight based on one hundred parts of the four component resinous system.
Catalysts are incorporated in small amounts into thermosetting polyester resins containing ethylenically unsaturated monomer to aid in curing or cross-linking the
unsaturated polyester with the monomer. Such catalysts are well known and may be similarly utilized in this invention to aid in curing the unsaturated polyester and monomer mixed with the low-profile thermoplastic polymer. Typical catalysts, for example include organic peroxide and peracids such as tertiary butyl perbenzoate, tertiary butyl peroctoate, benzoyl peroxide and the like. The amounts of catalysts may be varied with the molding process and similarly varied with the level and types of inhibitors utilized, in a manner well known in the art. In preferred embodiments the catalyst is present in amounts ranging from about 0.5 to about 2.5 parts, by weight, based on one hundred parts of the four component resinous system.
Curing of the composition is carried out under heat and pressure typically, in closed, preferably positive pressure type molds. Mold release agents may be added to the compositions to perform their normal function, as is well understood in the art, In preferred embodiments, the mold release agents are present in amounts ranging from about 0.5 to about 6.0 parts, by weight, based on one hundred parts of the four component resin system.
Fibers, fillers and pigments normally added to resin compositions can be likewise used in formulating the sheet molding composition of this invention. Reinforcing fibers or fibrous reinforcement is taken to mean glass fibers in one form or another, such as glass fabrics, chopped glass strands, chopped or continuous strand glass fiber mat; however, the terms also include reinforcing agents which may also be used if desired, for example, asbestos, cotton, synthetic organic fibers and metals. Fillers, usually inerts, and inorganic material useful with the compositions of the present invention include, for example, clay, talc calcium carbonate, silica, calcium silicate, and the like. In preferred embodiment the fillers are present in amounts
ranging from about 100 to about 300 parts, by weight, based on one hundred parts of the four component resinous syst
Examples of pigments include carbon black, iron oxide, titanium
dioxide, and the like, as well as organic pigments. In preferred
embodiments the pigments are present in amounts ranging from about 0 to about 4 parts, by weight, based on one hundred parts of the four
component resinous system.
The sheet molding composition of the present invention can be
prepared by mixing the components in a suitable apparatus at temperatures
which are conventional and known to those skilled in the art. Once the sheet molding composition is formulated, the composition can be molded
into thermoset articles having a desired shape. The actual molding cycle
will, or course, depend upon the exact composition being molded. In
preferred embodiments suitable molding cycles are conducted at temperatures ranging from about 250°-350° F for periods of time ranging from about 1/3 to about 5 minutes.
Examples 1 through 3 are given to show the improvements in
surface quality as measured by the LORIA technique, which is familiar to one skilled in the art of class "A" surface sheet molding compounds; surface energy measured by techniques familiar to the one skilled in the art of surface chemistry and adhesion to surface coating as measured by well
established techniques of cross-hatch peel. In the instance of surface quality measurement, a lower LORIA number rating signifies a smoother or a better surface. LORIA ratings of less than 85-90 are generally accepted
as smooth surface usage for body panel applications in the automotive industry. Surface energy measurements are viewed in clusters and within
the realm of similar base resin systems a higher surface energy has a
higher likelihood to give better adhesion to typical surface coatings.
Surface adhesion ratings are graded based on typical industry test
requirements. A lower grading signifies a higher degree of adhesion of the
substrate to the surface coating.
Example 1 depicts a system based on typical unsaturated polyester resin and low profile additive in use in various non-class "A" surface
automotive applications. The properties verify the fact that the sheet
molding compound is indeed not suitable for smooth, class "A" surface applications.
Example 2 depicts a system based on the same unsaturated polyester resin and low profile additive used in Example 2, but now
modified with the hydroxyl terminated polyether polyol low profile additive.
The properties show that the modification helps achieve a smooth, class
"A" surface but still falls short of surface coating adhesion requirements of painted appearance panels.
Example 3 depicts a system based on the same resin systems as in
Example 2 but further modified with glycidyl methacicylate. The properties
indicate that the smooth, class "A" surface finish has been retained and additionally the molded part has very good adhesion to the surface coating.
Example 4 depicts a system based on the same resin systems as in Example 3 but further modified with partially epoxidized soybean oil. The
properties indicate that the smooth class "A" surface has been retained while additionally the molded part has very good adhesion to the surface coating.
Example 1 :
Unsaturated polyester resin 50 parts
Low profile additive 50 parts
Filler 200 parts
Surface energy 38.9 dynes/cm Adhesion Grade 4
LORIA 180 Remarks: Poor class "A" surface
Poor adhesion properties
Example 2:
Unsaturated polyester resin 50 parts
Low profile additive (conventional & 39 parts hydroxyl terminated polyether blend Filler 200 parts Surface Energy 27.4 dynes/cm
Adhesion Grade 4
LORIA 60
Remarks: Good class "A" surface Poor adhesion
Example 3:
Unsaturated polyester resin "A" 50 parts
Low profile additive (conventional & 39 parts
hydroxyl terminated polyether blend
Glycidyl Methacrylate 2 parts
Filler 200 parts
Surface Energy 45 dynes/cm
Adhesion Grade 0
LORIA 60
Remarks: Good Class "A" surface
Good Adhesion
Example 4:
Unsaturated polyester resin "A" 50 parts
Low profile additive (conventional & 39 parts
Epoxidized soybean oil 2 parts
Filler 200 parts
Surface Energy
Adhesion Grade 0
LORIA 84
Remarks: Good Class "A" surface
Good Adhesion
One skilled in the art will readily recognize that certain specific
Example 5:
Unsaturated Polyester Resin (Orthphathalic acid based) 50 parts
Low profile additive
(conventional and hydroxyl terminated polyether blend) 42.25 parts
Epoxidized soybean oil 1.00 parts
Filler 200 parts
Surface Energy 38.3 dynes/cm
Adhesion Grade 0
LORIA 91
Remarks: Good Class "A" surface Good adhesion
Example 6:
Unsaturated Polyester Resin (Orthophathalic acid based) 50 parts
Low profile additive
(conventional and hydroxyl terminated polyether blend) 42.25 parts
Epoxidized soybean oil 3.0 parts
Filler 200 parts
Surface Energy 41 .3 dynes/cm
Adhesion Grade 0
LORIA Not measured
Appearance excellent surface smoothness
Remarks: Good Class "A" surface Good adhesion
Example 7:
Unsaturated Polyester Resin (Orthophathalic acid based) 50 parts
Low profile additive
(conventional and hydroxyl terminated polyether blend) 42.25 parts
Epoxidized methyl linseed oil 2.00 parts
Filler 200 parts
Surface Energy 37.1 dynes/cm
Adhesion Grade 0
LORIA 88
Remarks: Good Class "A" surface Good adhesion
Example 8:
Unsaturated Polyester Resin (Propylene glycol based) 50 parts
Low profile additive
(conventional and hydroxyl terminated polyether blend) 45.25 parts
Epoxidized linseed oil 2.0 parts
Filler 200 parts
Surface Energy 36.5 dynes/cm
Adhesion Grade 0
LORIA 83
Remarks: Good Class "A" surface Good adhesion
One skilled in the art will readily recognize that certain specific details shown in the foregoing specification and drawings are exemplary in nature and subject to modification without departing from the teachings of the disclosure. Various modifications of the invention discussed in the foregoing description will become apparent to those skilled in the art. All such variations that basically rely on the teachings through which the invention has advanced the art are properly considered within the spirit and scope of the invention.
Claims
1. A curable moldable thermosetting resin - containing composition for molding under pressure comprising:
(A) an unsaturated polyester resin having hydroxyl groups and carboxyl groups, having an acid number of less than 100 and an average molecular weight of between about 300 to
5,000;
(B) an aliphatically-unsaturated monomer;
(C) a catalyst capable of aiding in the polymerization of (A) and (B) ;
(D) a thermoplastic polymer;
(E) an additive having both aliphatically unsaturated bonds and polar functional groups;
(F) and adjuvants.
2. The curable moldable thermosetting resin-containing composition of claim 1 wherein (F) is selected from the group consisting of a filler, internal mold release agent and mixtures thereof.
3. The curable moldable thermosetting resin-containing composition of claim 2 wherein the filler includes a reinforcing
~ fiber and inert a particulate material.
4. The curable moldable thermosetting resin-containing composition of claim 1 wherein the additive (E) is selected from the group consisting of vermonia oil, vernolic acid esters, epoxidized vegetable oils, epoxidized soybean fatty acid esters, expoxidized linseed fatty acid esters, glycidyl methacrylate, glycidyl acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, tetrabromo bisphenol A diacrylate and mixtures thereof.
5. The curable moldable thermosetting resin-containing composition of claim 4 wherein the thermoplastic polymer (D) is selected from the group consisting of polyvinyl acetate, polymethylacrylate, polyurethane, polycaprolactone, cellulose acetate butyrate polymer, and mixtures thereof.
6. The curable moldable thermosetting resin-containing composition of claim 5 wherein the aliphatically-unsaturated monomer (B) is selected from the group consisting of styrene, methyl-styrene and mixtures thereof.
7. The curable moldable thermosetting resin-containing composition of claim 1 wherein the additive (E) is present in a quantity of between 0.2% to 10% by weight of the total amount of unsaturated polyester (A) and thermoplastic polymer (D) .
8. The curable moldable thermosetting resin-containing composition of claim 7 wherein the thermoplastic polymer (D) comprises a hydroxyl terminated polyether.
9. The curable moldable thermosetting resin-containing composition of claim 8 wherein the hydroxyl terminated polyether has a molecular weight of 200-4000.
10. The curable moldable thermosetting resin-containing composition of claim 5 wherein the thermoplastic polymer (D) is present in a quantity of between 1% to 10% by weight of the total amount of unsaturated polyester resin (A) and tήe thermoplastic polymer (D) .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU78455/94A AU7845594A (en) | 1993-09-28 | 1994-09-28 | Additives to improve surface characteristics of unsaturated polyester molding composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12785793A | 1993-09-28 | 1993-09-28 | |
| US08/127,857 | 1993-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1995009202A1 true WO1995009202A1 (en) | 1995-04-06 |
Family
ID=22432325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1994/010962 Ceased WO1995009202A1 (en) | 1993-09-28 | 1994-09-28 | Additives to improve surface characteristics of unsaturated polyester molding composition |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU7845594A (en) |
| WO (1) | WO1995009202A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5731035A (en) * | 1995-09-22 | 1998-03-24 | Cook Composites And Polymers | Process for making a paintable polymer article |
| US5900311A (en) * | 1994-03-23 | 1999-05-04 | Cook Composites And Polymers Co. | Thermosetting polyester composites prepared via vacuum-assisted technique with smooth surface appearance |
| WO2009071508A1 (en) * | 2007-12-03 | 2009-06-11 | Wacker Chemie Ag | Radically cross-linkable polymer compositions containing epoxy-functional copolymers |
| WO2010066781A1 (en) * | 2008-12-10 | 2010-06-17 | Wacker Chemie Ag | Graft copolymers and use thereof as low-profile additives |
| EP3652251A4 (en) * | 2017-07-11 | 2020-12-30 | Queen's University At Kingston | BIOBASED ADDITIVE FOR THERMOPLASTIC POLYESTER |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4245059A (en) * | 1973-08-29 | 1981-01-13 | Mitsubishi Rayon Co., Ltd. | Unsaturated polyester composition for molding compound and coated molded article thereof |
| US4472544A (en) * | 1982-07-27 | 1984-09-18 | Cdf-Chimie S.A. | Anti-shrink additive for unsaturated polyester, its fabrication process, and anti-shrink compositions |
| US4673706A (en) * | 1981-02-24 | 1987-06-16 | Union Carbide Corporation | Polyester molding compositions |
-
1994
- 1994-09-28 AU AU78455/94A patent/AU7845594A/en not_active Abandoned
- 1994-09-28 WO PCT/US1994/010962 patent/WO1995009202A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4245059A (en) * | 1973-08-29 | 1981-01-13 | Mitsubishi Rayon Co., Ltd. | Unsaturated polyester composition for molding compound and coated molded article thereof |
| US4673706A (en) * | 1981-02-24 | 1987-06-16 | Union Carbide Corporation | Polyester molding compositions |
| US4472544A (en) * | 1982-07-27 | 1984-09-18 | Cdf-Chimie S.A. | Anti-shrink additive for unsaturated polyester, its fabrication process, and anti-shrink compositions |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5900311A (en) * | 1994-03-23 | 1999-05-04 | Cook Composites And Polymers Co. | Thermosetting polyester composites prepared via vacuum-assisted technique with smooth surface appearance |
| US5731035A (en) * | 1995-09-22 | 1998-03-24 | Cook Composites And Polymers | Process for making a paintable polymer article |
| WO2009071508A1 (en) * | 2007-12-03 | 2009-06-11 | Wacker Chemie Ag | Radically cross-linkable polymer compositions containing epoxy-functional copolymers |
| CN101883823A (en) * | 2007-12-03 | 2010-11-10 | 瓦克化学股份公司 | Radically cross-linkable polymer compositions containing epoxy-functional copolymers |
| WO2010066781A1 (en) * | 2008-12-10 | 2010-06-17 | Wacker Chemie Ag | Graft copolymers and use thereof as low-profile additives |
| US8952096B2 (en) | 2008-12-10 | 2015-02-10 | Wacker Chemie Ag | Graft copolymers and use thereof as low-profile additives |
| EP3652251A4 (en) * | 2017-07-11 | 2020-12-30 | Queen's University At Kingston | BIOBASED ADDITIVE FOR THERMOPLASTIC POLYESTER |
| US11535745B2 (en) | 2017-07-11 | 2022-12-27 | Queen's University At Kingston | Biobased additive for thermoplastic polyesters |
| US11859081B2 (en) | 2017-07-11 | 2024-01-02 | Queen's University At Kingston | Biobased additive for thermoplastic polyesters |
Also Published As
| Publication number | Publication date |
|---|---|
| AU7845594A (en) | 1995-04-18 |
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