WO2000040634A2 - Resines epoxydes modifiees pour collage du papier - Google Patents

Resines epoxydes modifiees pour collage du papier Download PDF

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Publication number
WO2000040634A2
WO2000040634A2 PCT/US1999/030347 US9930347W WO0040634A2 WO 2000040634 A2 WO2000040634 A2 WO 2000040634A2 US 9930347 W US9930347 W US 9930347W WO 0040634 A2 WO0040634 A2 WO 0040634A2
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WO
WIPO (PCT)
Prior art keywords
group
alkyl
resin
acid
bisphenol
Prior art date
Application number
PCT/US1999/030347
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English (en)
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WO2000040634A3 (fr
Inventor
Angie H. Ma
Tuyen T. Nguyen
Original Assignee
Hercules Incorporated
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 Hercules Incorporated filed Critical Hercules Incorporated
Priority to AU23722/00A priority Critical patent/AU2372200A/en
Publication of WO2000040634A2 publication Critical patent/WO2000040634A2/fr
Publication of WO2000040634A3 publication Critical patent/WO2000040634A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/52—Epoxy resins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • the present invention relates to hydrophobically modified epoxy resins and more particularly it relates to such resins made by the reaction of a polyepoxide with an epoxide reactable hydrophobic reactant such as fatty acid, rosin acid, alkyl phenol; and optionally a chain extender such as a polyacid, polyphenol; and optionally a modifier such as an organic acid, or amine, or a phenol compound.
  • a polyepoxide reactable hydrophobic reactant such as fatty acid, rosin acid, alkyl phenol
  • a chain extender such as a polyacid, polyphenol
  • a modifier such as an organic acid, or amine, or a phenol compound.
  • Epoxy resins that contain a hydrophobic group have been described in USP 3,459,715 and 5,677,397.
  • an unsaturated fatty acid was reacted with an olefin-reactive anhydride such as maleic anhydride to give a polycarboxylic acid mixture.
  • This mixture is then treated with epichlorohydrin to form the epoxy.
  • USP 5,677,397 describes the making of epoxy resin with hydrophobic group from alkylated phenol. In this type of epoxy resin the alkylated phenol is part of the main chain of the epoxy resin.
  • a hydrophobically modified epoxy resin comprising (a) a polyfunctional epoxy resin backbone optionally chain extended with at least one difunctional group, and at least one hydrophobic moiety.
  • a process for preparing a hydrophobically modified epoxy resin comprising (a) providing polyepoxide reactant, (b) providing epoxide reactablde hydrophobic reactant, (c) optionally poviding chain extender reactant, (d) optionally providing modifier reactant, and (e) reacting said reactants.
  • sizing agents for paper and paper sized with such sizing agents are provided according to the present invention.
  • a hydrophobically modified epoxy resin comprising (a) a polyfunctional epoxy resin backbone optionally chain extended with at least one difunctional group, and (b) at least one hydrophobic moiety has been found to be an effective sizing agent for paper.
  • Polyfunctional epoxy resin is the main backbone of the sizing component.
  • Epoxies made from the reaction of epichlorohydrin with a polyhydroxy compound, a polyamino compound, a hydroxy amino compound are useful for this application.
  • Some of such epoxies are: diglycidyl ether of bisphenol A (Epon 828, Epon 1001 , Epon 1009 from Shell Chemical Co., DER 331 , DER 31 , DER 334 from Dow Chemical Co., EPN 1138 from Ciba Geigy Corp.), diglycidyl ethers of 4,4'- dihydroxydiphenyl methane 4,4'-dihydroxydiphenyl sulfone, resorcinol, biphenol, dihydroxydiphenyl sulfide, 4,2'-biphenol, tris(4-hydroxyphenyl)methane, 1 ,1,2,2 tetrakis(hydroxy-phenyl)methane, pentaerythr
  • Some of the commercially available epoxy novolaks are: D.E.N. 431 , D.E.N. 438, D.E.N. 485 (Dow Chemical Co.), ECN 1138, ECN 1235, ECN 1273, ECN 1299 (Ciba-Geigy Corporation).
  • Epoxy adducts of epichlorohydrin and amines are also useful such as N,N- 5 diglycidyl aniline, N,N-diglycidyl toluidine, N,N,N ,N -tetraglycidylbis(methylamino)- cyclohexane, N,N,N ,N ,-tetraglycidyl-4,4'-di-aminodiphenyl methane, N,N,N ,N - tetraglycidyl-3,3'diaminodiphenyl sulfone, N,N -dimethyl-N,N -diglycidyl- 4,4'diaminodiphenyl methane.
  • epoxies of this type include Araldite MY-720 (Ciba-Geigy Corp.), PGA-C and PGA-X (Sherwin-Williams Co., 0 Chicago, Illinois), Glyamine 125 and Glyamine 135 (F. I. C. Corp., San Francisco, CA)
  • the hydrophobic moiety of the hydrophobically modifed epoxy resin can be an alkyl phenol, and/or an alkylated monocarboxylic acid.
  • the alkyl group can be any alkyl group with a number of carbon atoms from 1 to 40.
  • the alkyl phenol may 5 also be substituted with a halide (I, Br, Cl, F), -NO 2 , -SO 3 H, -SO 2 H, -PO 3 H, - COOH, an aryl group, -OR or another alkyl group.
  • the carboxylic acid may be of alkyl carboxylic (C1-C40), or an alkaryl carboxylic acid.
  • Rosin acids and fluorinated carboxylic acid with a number of carbon atoms from 1 to 40 are also expected to provide both water and oil repellency.
  • the preferred alkyl phenol component is dinonyl phenol and the preferred alkylated monocarboxylic acid is stearic acid.
  • the epoxy backbone may be chain extended with a difunctional group such as a bisphenol, or dicarboxylic acid.
  • a difunctional group such as a bisphenol, or dicarboxylic acid.
  • Any known bisphenol or dihydroxyaryl compound can be used. Some of these compounds are: bisphenol A, bisphenol F, 5 rescorcinol, hydroquinone, dihydroxy napthalene, 4,4'-dihydroxydiphenyl sulfone, 4,4' dihydroxydiphenyl cyclohexane, 4,4'-dihydroxy-diphenyl ethane, 4,4'dihydroxy benzophenone, 4,4'-dihydroxydiphenyl ether etc. All of the dihydroxy compounds described in USP 4,925,910 are suitable, and the disclosure of USP 4,925,910 is hereby incorporated by reference. These dihydroxy compounds have the general o formula
  • R 4 (R 3 and R 4 are different when n and p are simultaneously O) or
  • R and R 2 are each alkyl or alkoxy, each of 1 to 6 carbon atoms
  • R 3 and R 4 are each hydrogen, alkyl of 1 to 6 carbon atoms, aryl or halogen-substituted alkyl of 1 to 4 carbon atoms
  • m is 0 or 1
  • n and p are 0, 1 , 2, 3 or 4.
  • the dicarboxylic acid may come from the following structure:
  • R benzenoid, napthalenoid, anthracenoid, alkyl (linear, cyclic, cycloaromatic, branched) having from 1 to 40 carbon atoms.
  • a mixed difunctional carboxylic acid and a phenolic can also be used such as hydroxy benzoic acid, hydroxy napthoic acid, hydroxy anthracenoic acid etc.
  • the hydrophobically modified epoxy resin of the present invention can optionally be further modified with an organic acid, or amine or phenolic compound, such as diacids, diamines and polyphenols.
  • the mixture of epoxy and chain extender can also be modified with a primary amine of the formula R-NH 2 where R is an organic moiety having from 1 to 30 carbon atoms and secondary amines of the formula R ⁇ NH where R, and R 2 can be the same or different organic moiety having from 1-30 carbon atoms.
  • the mole ratio of polyfunctional epoxy resin to hydrophobic moiety generally is at least about 0.1 :1. preferably about 1 :0.8.
  • the mole ratio can be up to about
  • additives that contain epoxy group or epoxy reactive group can also be added to the formulation to impart other functionalities such as cationic charge and aldehyde.
  • An example of this is the addition of Dow quat, glycidyltrimethylammonium chloride available from Dow Chemical Co. and 4-hydroxy benzaldehyde.
  • This modification utilities the same chemistry that is involved in the reaction between an epoxide and a nucleophile. The purpose of this modification is not hydrophobic modification but to provide other properties that are useful for a paper making application such as cationic charge, and cellulose reactive group.
  • the modified epoxy can be made from a polyepoxide, one or more than one hydrophobe modifier, and a chain extender by heating. Sometimes a catalyst can be added to speed up the reaction. Catalysts such as ethyltriphenyl phosphonium iodide, imidazole, trialkyl amine etc are suitable.
  • the synthesis of the resin of the present invention involves heating of a mixture of all ingredients and catalysts together at a temperature of at least about
  • the temperature can be up to about 200°C.
  • the reaction can be carried out with or without solvent. It is preferable to do the reaction without a solvent to minimize cost. When solvent is used it can be toluene, acetone, methylethyl, ketone, heptane, etc. Ingredients may be added at once or in stages to provide a needed molecular structure.
  • the general synthesis scheme of modified epoxy is illustrated in Scheme I.
  • a solution of the modified epoxy is dissolved in 1 ,2-dichloropropane (DCP) at the desired concentration.
  • DCP 1,2-dichloropropane
  • This solution is poured into an aluminum pan (6" x9").
  • a 5"X8" sheet of paper is dipped into this solution for 3 seconds and it is laid flat to dry. After 24 hrs, the sizing efficiency is determined using a Hercules Sizing Tester.
  • Sizing efficiency of modified epoxy is tested by solvent impregnation method since this test is independent of retention of the emulsion particles on paper.
  • the sizing efficiency is measured by the Hercules Size Test.
  • the Hercules Size Test is a standard test in the industry for measuring the degree of sizing. This method employs an aqueous dye solution as the penetrant to permit optical detection of the liquid front as it moves through the sheet. The apparatus determines the time required for the reflectance of the sheet surface not in contact with the penetrant to drop to a predetermined percentage of its original reflectance. All HST testing data reported measured the seconds to 80% reflection with 1% formic acid ink mixed with naphthol green B dye (Hercules Test Ink #2) unless otherwise noted. The use of this formic acid ink is a more severe test than neutral ink and tends to give faster test times. High HST values are better than low values. The amount of sizing desired depends upon the kind of paper being made and the system used to make it.
  • EPN 1138 a glycidyl ether of a low molecular weight novolak phenolic resin available from Ciba Geigy (10 g), nonyl phenol (11 g) and 0.2 g of ethyl triphenyl phosphonium iodide [ETPP1] was heated at 100° C for 3 hrs. The sizing was done using DCP as solvent and the sizing value is measured within 24 hrs of application to the paper. At 1 % loading of this material, unfilled paper gave
  • the sample was dissolved in propylene dichloride (PDC) and sized on filled and unfilled paper. Sizing test was performed within 24 hrs of application. At 1 % loading of this material, unfilled paper gave 3 sec. , filled paper gave 9 sec.
  • PDC propylene dichloride
  • Example 3 A mixture of EPN 1138 (5 g), stearic acid (5.9 g) and ETPPI (0.1) was heated at 130° C for 4 hrs. A solid was formed with a softening point at 45° C. At 1% loading of this material, unfilled paper gave 12 sec, and filled paper gave 17 sec. HST.
  • Example 7 A mixture of EPN 1138 (10 g), abietic acid (18 g) and ETPPI (0.2 g) was heated together at 140° C for 4 hrs. A solid with softening point of 108° C was obtained. At 0.1 % loading of this material, unfilled paper gave 580 sec and filled paper gave 140 sec of HST within 24 hrs of application. Natural aged samples (2 weeks) gave 736 sec and 140 sec of HST, respectively.
  • Example 12 A mixture of EPN 1138 (5 g), nonyl phenol (4.9 g), t-phthalic acid (0.46 g) and
  • ETPPI (0.1g) was heated at 130°C for 5 hrs. A solid with softening point of 47°C was obtained. At 0.25% loading of this material, unfilled paper gave 64 sec and filled paper gave 100 sec of HST.
  • Example 20 A mixture of EPN 1138 (5 g), nonyl phenol (4.3 g), bi-naphthol (1.2 g) and
  • ETPPI (0.1 g) was heated at 130°C for 3.5 hrs. A solid with a softening point of 55°C was obtained. At 0.25% loading of this solid, unfilled paper gave 245 sec and filled paper gave 272 sec of HST. After two weeks, the paper gave 240 sec and 280 sec of HST, respectively.
  • Example 8 EPN 1138/Pamite 90 1/0.6 0.1%
  • Example 11 PN 1138/NP/BPA 1/0.8/0.1 0.25%
  • Example 12 PN 1138/NP/PthA 1/0.8/0.1 0.25%
  • Example 13 PN 1138/NP/BPA 1/0.7/0.15 0.25%
  • Example 14 PN 1138/NP/ADP 1/0.7/0.15 0.25%
  • Example 15 PN 1138/NP/BPA 1/0.7/0.16 0.25%
  • Example 16 PN 1138/SA/BPA 1/0.7/0.16 0.25%
  • Example 17 PN 1138/DNP/BPA 1/0.7/0.16 0.25%
  • Example 18 PN 1138/NP/SBA 1/0.7/0.15 0.25%
  • Example 19 PN 1138/AA/BP 1/0.7/0.15 0.25%
  • Example 20 PN 1138/NP/BNP 1/0.7/0.15 0.25%
  • Example 21 PN 1138/NP//BNP 1/0.7/0.15 0.25%
  • Example 21 PN 1138/NP//BPA
  • Example 26 PN 1138/NP/2-NAP 1/0.7/0.15 0.25%
  • Example 27 EPN 1138/Stearis Acid/Bisphenol A/Decyl amine (1/0.62/0.08/0.09)
  • ETPPI (0.15 g) was heated at 145°C for 10 hrs. The temperature of the reaction mixture was lowered to 80°C, and adipic acid (0.97 g) was added. The mixture was kept at 80°C for 2 hrs. At 0.25% loading of this material, filled paper gave 54 sec and unfilled paper gave 207 sees of HST. After 2 weeks, the HST values became 213 sec and 388 sec, respectively.
  • Example 30 EPN 1138/Stearic Acid/Bisphenol A/hexyl amine (1/0.62/0.08/0.12) A mixture of EPN 1138 (8.89 g), stearic acid (8.7 g), bisphenol A (0.90 g),
  • ETPPI (0.07 g) and hexyl amine (0.06 g) was heated at 145°C for 10 hrs. At 0.25% loading of this material, filled paper gave 241 sec and unfilled paper gave 545 sees of HST. After 2 weeks, the HST values became 215 sec and 743 sec, respectively.
  • Example 31 EPN 1138/Stearic Acid/Bisphenol A/dibutyl amine(1/0.62/0.08/0.08)
  • EPN 1138/Stearic Acid/Bisphenol A/4-Hydroxybenzaldehyde (1/0.5/0.2/0.15) A mixture of EPN 1138(20 g), stearic acid (15.8 g), bisphenol A (3.8 g),
  • ETPPI (0.15 g) and 4-hydroxybenzaldehyde (2.7 g) was heated at 145°C for 10 hrs. At 0.25% loading of this material, filled paper gave 231 sec and unfilled paper gave 477 sees of HST. After 2 weeks, the HST values became 246 sec and 592 sec, respectively.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une résine époxyde rendue hydrophobe comportant (a) un squelette de résine époxyde polyfonctionnel à chaîne éventuellement allongée par au moins un groupe difonctionnel, et (b) au moins une fraction hydrophobe, cette résine convenant particulièrement bien comme agent de collage pour papier.
PCT/US1999/030347 1998-12-30 1999-12-17 Resines epoxydes modifiees pour collage du papier WO2000040634A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU23722/00A AU2372200A (en) 1998-12-30 1999-12-17 Modified epoxies for paper sizing

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22483898A 1998-12-30 1998-12-30
US09/224,838 1998-12-30

Publications (2)

Publication Number Publication Date
WO2000040634A2 true WO2000040634A2 (fr) 2000-07-13
WO2000040634A3 WO2000040634A3 (fr) 2000-11-23

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001093482A (ja) * 1999-09-20 2001-04-06 Dainippon Printing Co Ltd ポリマー電池用包装材料
WO2015078072A1 (fr) * 2013-11-29 2015-06-04 中科院广州化学有限公司 Résine époxy amphiphile contenant du fluor, son procédé de préparation, et surface superamphiphobe fabriquée avec celle-ci
CN106592238A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种改性环氧树脂通用型碳纤维上浆剂、制备方法和应用
CN106592239A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种大丝束通用型碳纤维上浆剂、制备方法和应用
CN106592237A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种碳纤维用不饱和酸改性环氧树脂通用型上浆剂、制备方法和应用
CN106592236A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种小丝束通用型碳纤维上浆剂、制备方法及其应用
CN106592240A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种碳纤维用改性环氧树脂通用型上浆剂、制备方法及其应用
CN109912780A (zh) * 2017-12-13 2019-06-21 深圳市百安百科技有限公司 一种低粘度耐热环氧树脂的制备方法
CN115677979A (zh) * 2022-11-15 2023-02-03 河北昊泽化工有限公司 一种环保抗水剂的制备方法及生产设备

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0160622A2 (fr) * 1984-05-02 1985-11-06 Ciba-Geigy Ag Compositions contenant des esters de résines époxydes allongées
EP0253404A2 (fr) * 1986-07-18 1988-01-20 The Dow Chemical Company Revêtements à base d'époxydes à formation de film contrôlée, appliqués par électrodéposition cathodique
DE4112144C1 (fr) * 1991-04-13 1992-07-09 Ruetgerswerke Ag, 6000 Frankfurt, De
EP0568908A2 (fr) * 1992-05-06 1993-11-10 BASF Lacke + Farben AG Composés époxydes polyvalents

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0160622A2 (fr) * 1984-05-02 1985-11-06 Ciba-Geigy Ag Compositions contenant des esters de résines époxydes allongées
EP0253404A2 (fr) * 1986-07-18 1988-01-20 The Dow Chemical Company Revêtements à base d'époxydes à formation de film contrôlée, appliqués par électrodéposition cathodique
DE4112144C1 (fr) * 1991-04-13 1992-07-09 Ruetgerswerke Ag, 6000 Frankfurt, De
EP0568908A2 (fr) * 1992-05-06 1993-11-10 BASF Lacke + Farben AG Composés époxydes polyvalents

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001093482A (ja) * 1999-09-20 2001-04-06 Dainippon Printing Co Ltd ポリマー電池用包装材料
WO2015078072A1 (fr) * 2013-11-29 2015-06-04 中科院广州化学有限公司 Résine époxy amphiphile contenant du fluor, son procédé de préparation, et surface superamphiphobe fabriquée avec celle-ci
CN106592240A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种碳纤维用改性环氧树脂通用型上浆剂、制备方法及其应用
CN106592239A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种大丝束通用型碳纤维上浆剂、制备方法和应用
CN106592237A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种碳纤维用不饱和酸改性环氧树脂通用型上浆剂、制备方法和应用
CN106592236A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种小丝束通用型碳纤维上浆剂、制备方法及其应用
CN106592238A (zh) * 2015-10-14 2017-04-26 中国石油化工股份有限公司 一种改性环氧树脂通用型碳纤维上浆剂、制备方法和应用
CN106592240B (zh) * 2015-10-14 2020-09-04 中国石油化工股份有限公司 一种碳纤维用改性环氧树脂通用型上浆剂、制备方法及其应用
CN106592237B (zh) * 2015-10-14 2020-09-04 中国石油化工股份有限公司 一种碳纤维用不饱和酸改性环氧树脂通用型上浆剂、制备方法和应用
CN106592238B (zh) * 2015-10-14 2020-09-04 中国石油化工股份有限公司 一种改性环氧树脂通用型碳纤维上浆剂、制备方法和应用
CN109912780A (zh) * 2017-12-13 2019-06-21 深圳市百安百科技有限公司 一种低粘度耐热环氧树脂的制备方法
CN109912780B (zh) * 2017-12-13 2021-08-06 深圳市百安百科技有限公司 一种低粘度耐热环氧树脂的制备方法
CN115677979A (zh) * 2022-11-15 2023-02-03 河北昊泽化工有限公司 一种环保抗水剂的制备方法及生产设备

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AU2372200A (en) 2000-07-24

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