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WO1995009201A1 - Compositions polyester insaturees modifiees par polyuree - Google Patents

Compositions polyester insaturees modifiees par polyuree Download PDF

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Publication number
WO1995009201A1
WO1995009201A1 PCT/US1994/010880 US9410880W WO9509201A1 WO 1995009201 A1 WO1995009201 A1 WO 1995009201A1 US 9410880 W US9410880 W US 9410880W WO 9509201 A1 WO9509201 A1 WO 9509201A1
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WO
WIPO (PCT)
Prior art keywords
thermosetting resin
containing composition
resin
moldable thermosetting
curable moldable
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
Application number
PCT/US1994/010880
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English (en)
Inventor
Probir Guha
Hong-Son Ryang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cambridge Ind Co
Original Assignee
Cambridge Ind Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cambridge Ind Co filed Critical Cambridge Ind Co
Priority to AU78438/94A priority Critical patent/AU7843894A/en
Publication of WO1995009201A1 publication Critical patent/WO1995009201A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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 present invention relates to molding compounds made from unsaturated polyester resins and more specifically to a thickener system
  • polyester resins has been due in large part to the development of thickenable systems.
  • An example of such a system was disclosed by Fisk in U.S. Patent No. 2,628,209.
  • the system consisted of adding a metallic or hydroxide to an unsaturated polyester resin. Amounts of such metallic oxide or hydroxide
  • thickening agents of between one hundred and three hundred percent, based
  • BMC bulk molding compounds
  • 4,535,110 involves the use of metallic oxide or hydroxide and polyisocyanate as a dual thickening system.
  • the polyisocyanate reacts with water and/or acid groups of the polyester resin to produce carbon dioxide which evolves therefrom causing blisters and other imperfections in
  • the present invention consists of a maturated moldable thermosetting resin-containing composition for molding under pressure at an elevated temperature in which the curable resin system consists essentially of (A) an unsaturated polyester resin having hydroxyl groups and carboxyl groups and (B)(1 ) an organic polyisocyanate, (B)(2) a metallic oxide or hydroxide, and
  • thermoplastic additives for low-shrink control is an optional part of this invention, and (G) also includes additives used to reduce matrix viscosity and modify resin cure gel times.
  • the present invention encompasses a maturated moldable thermosetting resin-containing composition for molding under pressure at an
  • thermosetting composition consists essentially of the following ingredients: (A) a thermosetting unsaturated polyester resin, (B) a ternary
  • thickening system (C) an aliphatically unsaturated monomer, (D) a free radical polymerization catalyst, (E) an internal mold release agent, and either or both of (a) reinforcing fibers and (b) inert fillers, and may in addition contain (F) a thermoplastic additive to produce molding compositions with low-shrink characteristics, and (G) viscosity reducers and additives to modify matrix viscosity and gel times.
  • items (E), (a), and (b) are optional but usual ingredients, whereas (F) and (G) are also optional but less usual ingredients.
  • the components (A) and (B), containing dispersed therein (C), (D), (G) and (E), constitute the curable resin binder which generally comprises at least about eight percent, and generally at least about ten percent, of the total weight of said composition.
  • the unsaturated polyester resin employed according to the present invention has (1 ) ratio of hydroxyl groups to carboxyl groups between about
  • the resin preferably has an
  • Said resin preferably has a molecular weight of about 900 to 3,500.
  • unsaturated polyester comprises a condensation product of one or more dihydric alcohols and one or more ethylenically unsaturated polycarboxylic acids.
  • the resinous condensation product is ordinarily dissolved in an aliphatically unsaturated monomer, such as styrene, (reactant C herein) prior to use in the process of the invention.
  • the unsaturated polyester component of the four component resinous system comprises the polycondensation reaction product of one or more dihydric alcohols and one or more ethylenically unsaturated polycarboxylic acids.
  • polycarboxylic acid is generally meant the polycarboxylic or dicarboxylic acids or anhydrides, polycarboxylic or dicarboxylic acid halides,
  • 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,
  • polyesters 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.
  • propylene glycol 1,2-propane diol
  • dipropylene glycol diethylene glycol
  • 1 ,3- butanediol 1,3-butanediol
  • ethylene glycol 1,3-butanediol
  • glycerol 1,3-butanediol
  • unsaturated polyesters are the poly-condensation 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 or less of ethylene glycol) and maleic and/or fumaric acid; (4) propylene glycol, maleic and/or fumaric acids and dicyclopentadiene reacted with water.
  • dicyclopentadiene modified unsaturated polyester resins as described in the Pratt et al. U.S. Pat. No. 3,883,612. 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
  • 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
  • the unsaturated polyester is present in
  • This type of starting unsaturated polyester is prepared from propylene or ethylene glycol, maleic acid or anhydride, and phthalic or isophthalic acid, plus miscellaneous other glycols as set forth under A in the foregoing.
  • the ratio of maleate to phthalate is about 3:1.
  • Such products are representatively prepared by cooking together, for example, 0.75 mole of maleic acid or anhydride, 0.25 mole of isophthalic acid, and 1.1 mole of propylene glycol.
  • Such type unsaturated polyesters have the properties of being slightly more resilient than type A, stronger than type A, have a slightly lower heat resistance than type A, and are slightly less reactive than type A.
  • This type of unsaturated polyester is prepared from ethylene glycol or propylene glycol, maleic acid or anhydride, and isophthalic acid, plus miscellaneous other glycols as in A, the maleate-phthalate ratio in this case being about 2:1. Preparation is affected in substantially the same manner as given in the foregoing for Type B.
  • Such type resins are characterized by extreme toughness, higher elongation, low heat distortion, and a lower
  • resins are well known and are conventionally made by the condensation of at least one unsaturated dicarboxylic acid or anhydride and at least one glycol
  • suitable unsaturated dicarboxylic acids include alpha, beta ethylenically unsaturated dicarboxylic acids and their anhydrides such as fumaric acid, maleic acid, and maleic anhydride.
  • saturated polycarboxylic acids and their anhydrides include the phthalic acids, phthalic anhydride, succinic acid, adipic acid and itaconic acid.
  • Other polycarboxylic acids usable herein include citric acid, pyromellitic acid and trimesic acid.
  • the preferred glycols usable herein to make the polyester resin are the alkylene glycols such as ethylene glycol, propylene glycol, neopentyl glycol, butylene glycol, and bisphenol A, all as is well known in the art. Either the dicarboxylic acids or the glycols may be halogenated to reduce the flammability of molded articles.
  • organic polyisocyanates preferred for the present invention also contain organic polyisocyanates.
  • isocyanate terminated prepolymers and quasi-prepolymers which are prepared by reacting the said organic polyisocyanates and preferably a di- isocyanate with a polyol, using standard procedures.
  • the polyols could be selected from polyester polyols, polyester polyols, polycaprolactone polyols, and, indeed, any hydroxyl terminated oligomer. In preparing the isocyanate
  • the metallic oxide or hydroxide (B)(2) is selected from the group consisting of calcium and magnesium oxides and hydroxides and is employed in an amount sufficient to react with at least thirty percent but not more than seventy-five percent of the carboxyl groups present in the reaction.
  • the choice of metallic oxide or hydroxide is a matter of individual preference, and depends inter alia upon the particular polyester resin used and the exact manufacturing procedure employed for producing the molding composition, as is well known to one versed in the art.
  • Polyamine (B)(3) is selected from the group consisting of calcium and magnesium oxides and hydroxides and is employed in an amount sufficient to react with at least thirty percent but not more than seventy-five percent of the carboxyl groups present in the reaction.
  • the choice of metallic oxide or hydroxide is a matter of individual preference, and depends inter alia upon the particular polyester resin used and the exact manufacturing procedure employed for producing the molding composition, as is well known to one versed in the art.
  • Polyamine (B)(3) is selected from the group consisting of calcium and magnesium oxides and hydro
  • the polyamine preferred for the present invention is selected from the group consisting of aliphatic and alicyclic amines, including diethylene triamine, triethylene tetramine, hexamethylene diamine, 1 ,8-octane diamine, poly(oxypropylene) diamine, poly(oxyethylene) diamine, poly(oxypropylene) triamine, poly(oxyethylene) triamine, primary and secondary amine terminated polybutadiene, primary and secondary amine terminated polybutadiene
  • copolymers polyglycol amine, isophorone diamine, cyclohexane diamines, N- aminoethylpiperazine, diamino dicyclohexyl methane; and polyamide amines,
  • reaction products of dimerized and trimerized vegetable oil fatty acids with polyamines aromatic amines including toluene diamine, phenylene diamines, methylene dianiline, diaminodiphenyl ethers, diaminodiphenyl sulfones, amine terminated polyethers such as polyethylene oxide,
  • polyamines having a free secondary or primary amine concentration cf 0.2% to 20%, or more preferably 1 % to 5%, and a molecular weight of 50 to 5000, or more preferably 100 to 3000; the polyamine or blend of polyamines being present in concentrations of 1 % to 15%, or more preferably 2% to 10% based on the quantities of unsaturated polyester present in the formulation; the polyamine or blend of polyamines being present in quantities sufficient to react with 50% to 150% of the quantities of polyisocyanate present in the formulation.
  • Aliphatically-unsaturated monomer (C) According to the invention, the reaction product, unsaturated resin A, is mixed with (C) a co-polymerizable aliphatically-unsaturated monomer.
  • the aliphatically-unsaturated monomer (C) is ordinarily present in an amount to
  • reaction product also contains therein
  • the catalyst (D) is preferably
  • Such a free radical polymerization catalyst is added to the uncured composition so that, upon heating to the catalyst activation temperature, the addition-type cross-linking polymerization reaction will commence between
  • Such catalyst is usually used in an amount in the range of about 0.1 to 3.0 parts per 100 parts of total monomer and resin.
  • free radical generating polymerization catalysts are usable, such as lauroyl peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, and 2,4- dichlorobenzoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, and others including dicumyl peroxide, 2,2'-bis(4,4'-ditertiary butyl peroxy cyclohexyl propane), ditertiary butyl peroxide, cumene hydroperoxide, tertiary butyl cumyl peroxide, and tertiary butyl perbenzoate.
  • Internal mold release agents such as zinc stearate, calcium stearate, magnesium stearate, organic phosphate esters, and other organic liquid internal mold release agents may be employed, as is well known in the art.
  • the fiber reinforcement may be present in an amount of about 5 to about 25 weight percent for bulk molding compositions and about 10 to 70 weight percent for sheet molding compositions.
  • the fiber employed is preferably fiberglass.
  • the amount of reinforcing fiber is preferably about 25-70 weight percent for sheet molding
  • reinforcing fibers are available for use herein to form the sheet molding compound and bulk molding compound such as glass
  • Fibers and whiskers such as steel fibers and whiskers, boron fibers and whiskers, and graphite fibers and whiskers.
  • organic fibers may be used. Glass fibers are the most desirable fibers for most applications because of their low cost and high strength.
  • Non-Reinforcing Fillers may be, if desired, and generally are added to the uncured composition to reduce overall material costs without sacrificing a significant degree of desirable physical properties in the final product or to impart specific properties to the compound. Many different types of fillers can be
  • inorganic fillers e.g., silicate, asbestos, calcium carbonate,
  • these fillers may be added in amounts ranging from about twenty parts to one thousand parts by weight per one hundred parts of the pure polyester resin. When used alone without reinforcing fiber, the filler is employed in an amount of about fifty to about eighty weight percent for bulk molding compositions.
  • the molding compositions of the invention may include (F), a low-
  • shrink additive consisting essentially of a thermoplastic polymer, ordinarily added dissolved in styrene or other unsaturated monomer (C), said low-shrink additive preferably being present in an amount of about ten to fifty-five parts by weight per one hundred parts of resin (A).
  • This low-shrink additive when optionally employed, is generally added to the combination of the unsaturated polyester resin and the ethylenically unsaturated polymerizable liquid monomer, and may be in the form of a thermoplastic powder solubilized in part or all of the polymerizable liquid monomer employed.
  • Such low-shrink thermoplastic based additives are described in U.S. Pat. No.
  • thermoplastic polymers or copolymers (F) which may be employed to obtain low-shrink characteristics, except that for purposes of the present invention it is not necessary that such thermoplastic polymer or copolymer (F) be of a nature which yields an optically heterogeneous cured composition.
  • inhibitors were used and the normal free radical initiators were omitted to enable one to make viscosity measurements over the entire temperature range to illustrate the efficacy of the dual
  • the starting unsaturated polyester is dispersed in the
  • a suitable internal lubricant such as zinc
  • stearate and a suitable amount of free radical catalyst, such as a peroxide, are introduced into the mixture.
  • Optional ingredients include inorganic filler such as calcium carbonate, thermoplastic resin for low shrink, and pigment for coloration.
  • the ternary thickener system of the present invention is added thereto.
  • the ternary thickener system ingredients are added simultaneously to the starting unsaturated polyester dispersed in the aliphatically unsaturated monomer. That is, a polyamine is added to react with an isocyanate to prevent the isocyanate from undergoing undesirable side reactions with, for example, H 2 O to generate CO 2 gas causing blistering of the molded part while increasing the viscosity of the matrix through a chain extension reaction
  • glass-filled and maturated molding composition is then molded under conditions of increased heat and pressure, to produce the desired molded
  • the molding composition or compound may be subjected to the usual molding procedure under conditions of increased heat and pressure, and all of the foregoing is fundamentally well-established in the prior art.
  • the important aspect of the present invention is that, upon addition of the ternary thickening system of the invention to the original mixture and upon completion of impregnation of the glass and other fibers, the matrix rapidly builds viscosity attaining moldability stage more rapidly than conventional systems and systems described in the Epel patent. Further, the matrix upon completion of viscosity buiid maintains a relatively stable
  • the dispersion thereof in the aliphatically unsaturated monomer preferably simultaneously the thickeners are introduced into the polyester or polyester dispersion, which is usually the polyisocyanate, the aforementioned polyester resin compound is usually brought into intimate contact with a mass of reinforcing fibers.
  • This simultaneity is desirable, but less essential than previously, when employing the compositions of the present invention, so that the uncured resin and other constituents wet the surface of the individual fibers before the resin starts to maturate.
  • This technique provides the best possible bonding environment between the reinforcing fibers and the cured polyester resin.
  • the reinforcing fibers can be in the form of woven or nonwoven cloths or batts or in the form of bulk fibers either continuous or chopped.
  • SMC the fibers and resin matrix and the fibers and resin compound are processed under sufficient pressure to form an intimate dispersion of both components without gross breakage of the individual fibers, and this dispersion is then formed into a thin sheet. This is commonly
  • the newly formed sheets of wet mixture are extremely tacky, they are often covered on both sides with a thin, relatively nonporous film such as polyethylene film or polypropylene film and rolled up or otherwise stored for a sufficient length of time to permit maturation to take place. This may be from a few hours to twenty-four hours, during which time the stability and shelf life of the composition once again stabilizes, as already noted.
  • the sheet may be unrolled and the nonporous films stripped away to reveal a nontacky, rather flexible sheet of fiber containing thickened but not crosslinked polyester resin that is ready to be cut into a desired outline and stacked in layers in a compression molding press where it will be pressed into the desired configuration and heated to activate the free-radical generating catalyst to begin the crossiinking reaction between the polymerizable monomer and the unsaturated polyester resin.
  • This maturation of the unsaturated polyester resin composition takes place with the composition still in the uncured state.
  • the uncured or uncrosslinked polyester resin composition generally comprises a homogeneous blend of an unsaturated polyester resin with various other constituents as previously described and the background of which is generally found in U.S. Pat. No. 3,701 ,748. This maturation is generally conducted at room temperature or slightly above, according to the by now well-established skill of the art.
  • the maturated resin molding compound of this invention can be in the form of a bulk molding compound (BMC) or in the form of a sheet molding compound (SMC) as these compounds and other similar compounds are
  • BMC bulk molding compounds
  • DMC dough molding compounds
  • sheets of SMC compound are cut to the general outline of the article to be molded, are stacked in a predetermined number of layers, and are inserted into the cavity of a compression molding machine.
  • the machine is closed to form the layers into the desired configuration, and the layers are heated therein so that the thermosetting resin will crosslink and form a solid article, the crosslinking taking place through the aliphatic unsaturation in the polyester.
  • articles made by this technique include automobile body parts, appliance housings, furniture elements, tables and chairs, and luggage. Generally they comprise a cured polyester resin compound having at least one exposed surface.
  • the maturated compounds of this invention when used in molding flow properly into the mold and maintain the desired dispersion of fibers and/or fillers during both mold-filling operation and the curing cycle to produce articles that are characterized by excellent internal strength as well as excellent surface quality and a high degree of adhesion between the exposed surface of the article and an overlying paint or other covering film applied thereto.
  • fenders e.g., fenders, hood, grill opening panels, and fender extensions
  • deck lids deck lids; tailgates, valve covers, heat shields that are exposed to varying
  • reaction is utilized in crosslinking and curing the unsaturated polyester molecules with and through an ethylenically unsaturated polymerizable liquid monomer such as styrene or vinyl toluene in a free-radical, addition-type curing reaction along the lines fully described in U.S. Pat. No. 3,701 ,748, this crosslinking and curing taking place during the molding operation in which the composition or molding compound is heated and subjected to pressure so that curing or crosslinking and formation of a solid article will occur.
  • an ethylenically unsaturated polymerizable liquid monomer such as styrene or vinyl toluene
  • thermosetting resins present in the molding compositions of the invention takes place through the aliphatic unsaturation in the polyester and the ethylenically unsaturated polymerizable liquid monomers. It is to be understood that the invention is not to be limited to the exact
  • Example 1 Example 1
  • Examples 1 and 2 are provided to show improvements in initial viscosity build and shelf life stability obtained when the polyurea thickening mechanism is used without any changes in major ingredients.
  • Example 1 stays within the desirable processing window of 20 x 10 s cps to 45 x 10 s cps matrix viscosity for a period of 3 to 4 days, whereas an improvement as shown in Example 2 stays within the processing range for a considerably longer period of time.

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  • 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

Composition thermodurcissable moulable amenée à maturation contenant des résines destinées à être moulées sous pression à température élevée, dans laquelle le système de résine polymérisables consiste essentiellement (A) en une résine polyester insaturée comportant 5 groupes hydroxyles et (B)(1) en un polyisocynante organique, (B)(2) un oxyde ou hydroxyde métallique, et (B)(3) en une polyamine destinée à réagir avec le polyisocyanate, ledit produit de réaction contenant sous forme dispersée, (C) un monomère aliphatiquement insaturé, (D) un catalyseur de polymérisation à radicaux libres, (E) un agent de démoulage interne et soit l'un soit les deux composants suivant (a) des fibres renforçatrices et (b) des charges inertes. De plus, l'inclusion (F) d'additifs thermoplastiques permettant le réglage du faible retrait est facultative et comprend (G) des additifs pour réduire la viscosité matricielle et pour modifier les périodes de gel de polymérisation des résines.
PCT/US1994/010880 1993-09-28 1994-09-28 Compositions polyester insaturees modifiees par polyuree Ceased WO1995009201A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU78438/94A AU7843894A (en) 1993-09-28 1994-09-28 Polyeurea modified unsaturated polyester compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12784193A 1993-09-28 1993-09-28
US08/127,841 1993-09-28

Publications (1)

Publication Number Publication Date
WO1995009201A1 true WO1995009201A1 (fr) 1995-04-06

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PCT/US1994/010880 Ceased WO1995009201A1 (fr) 1993-09-28 1994-09-28 Compositions polyester insaturees modifiees par polyuree

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WO (1) WO1995009201A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7022754B2 (en) 2001-10-23 2006-04-04 Koito Manufacturing Co., Ltd. Unsaturated polyester resin composition, cured unsaturated polyester resin and lamp reflecting mirror base
EP2292675A1 (fr) 2009-09-08 2011-03-09 BYK-Chemie GmbH Polyurées comme agents régulateur de rhéologie
WO2019122213A1 (fr) 2017-12-21 2019-06-27 Byk-Chemie Gmbh Additif de régulation rhéologique antisédimentation contenant un groupe urée et un groupe uréthane
WO2019122222A1 (fr) 2017-12-21 2019-06-27 Byk-Chemie Gmbh Agents de contrôle de rhéologie, anti-affaissement, contenant des groupes urée
CN120424276A (zh) * 2025-07-07 2025-08-05 山东旺林新材料有限公司 一种改性脲溶液增稠光固化不饱和聚酯树脂及制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4683266A (en) * 1985-03-18 1987-07-28 Ashland Oil, Inc. Compositions thickened through urethane reaction
US5047455A (en) * 1987-09-16 1991-09-10 Basf Aktiengesellschaft Thickened molding compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4683266A (en) * 1985-03-18 1987-07-28 Ashland Oil, Inc. Compositions thickened through urethane reaction
US5047455A (en) * 1987-09-16 1991-09-10 Basf Aktiengesellschaft Thickened molding compositions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7022754B2 (en) 2001-10-23 2006-04-04 Koito Manufacturing Co., Ltd. Unsaturated polyester resin composition, cured unsaturated polyester resin and lamp reflecting mirror base
DE10249400B4 (de) * 2001-10-23 2007-07-12 Koito Manufacturing Co., Ltd. Ungesättigte Polyesterharzzusammensetzung, gehärtetes ungesättigtes Polyesterharz und Lampenreflektorspiegel-Unterlage
EP2292675A1 (fr) 2009-09-08 2011-03-09 BYK-Chemie GmbH Polyurées comme agents régulateur de rhéologie
WO2011029556A1 (fr) 2009-09-08 2011-03-17 Byk-Chemie Gmbh Polyurées comme agent de contrôle rhéologique
US9617371B2 (en) 2009-09-08 2017-04-11 Byk-Chemie Gmbh Polyureas as rheology control agents
WO2019122213A1 (fr) 2017-12-21 2019-06-27 Byk-Chemie Gmbh Additif de régulation rhéologique antisédimentation contenant un groupe urée et un groupe uréthane
WO2019122222A1 (fr) 2017-12-21 2019-06-27 Byk-Chemie Gmbh Agents de contrôle de rhéologie, anti-affaissement, contenant des groupes urée
US11702385B2 (en) 2017-12-21 2023-07-18 Byk-Chemie Gmbh Urea group containing anti-sagging rheology control agents
CN120424276A (zh) * 2025-07-07 2025-08-05 山东旺林新材料有限公司 一种改性脲溶液增稠光固化不饱和聚酯树脂及制备方法
CN120424276B (zh) * 2025-07-07 2025-10-28 山东旺林新材料有限公司 一种改性脲溶液增稠光固化不饱和聚酯树脂及制备方法

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