CN106366601A - Unsaturated polyester resin for anchoring agents - Google Patents

Unsaturated polyester resin for anchoring agents Download PDF

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Publication number
CN106366601A
CN106366601A CN201610743502.2A CN201610743502A CN106366601A CN 106366601 A CN106366601 A CN 106366601A CN 201610743502 A CN201610743502 A CN 201610743502A CN 106366601 A CN106366601 A CN 106366601A
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CN
China
Prior art keywords
parts
stirring
castor oil
polyester resin
unsaturated polyester
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.)
Pending
Application number
CN201610743502.2A
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Chinese (zh)
Inventor
李志业
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.)
Anhui Xinli Composite Material Co Ltd
Original Assignee
Anhui Xinli Composite Material Co Ltd
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 Anhui Xinli Composite Material Co Ltd filed Critical Anhui Xinli Composite Material Co Ltd
Priority to CN201610743502.2A priority Critical patent/CN106366601A/en
Publication of CN106366601A publication Critical patent/CN106366601A/en
Pending 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
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention discloses an unsaturated polyester resin for anchoring agents. The unsaturated polyester resin for anchoring agents is prepared from the following raw materials in parts by weight: 20-35 parts of itaconic acid, 2-10 parts of m-phthalic acid, 10-19 parts of abietic acid, 15-22 parts of acetic anhydride, 15-25 parts of dipropylene glycol, 8-16 parts of ethanediol, 10-30 parts of diethylene glycol, 25-45 parts of fumaric acid, 18-28 parts of vinyltoluene, 1-3 parts of modified castor oil, 2-6 parts of mesoporous molecular sieve, 1-4 parts of vapor-phase silicon dioxide and 0.5-1.5 parts of butyltrimethoxy silane. The unsaturated polyester resin for anchoring agents has the advantages of high rigidity, favorable wettability and small shrinkage.

Description

A kind of unsaturated polyester resin for Anchor Agent
Technical field
The present invention relates to unsaturated polyester resin technical field, more particularly, to a kind of unsaturated polyester (UP) tree for Anchor Agent Fat.
Background technology
Unsaturated polyester resin has excellent mechanical performance, electrical property and resistance to chemical corrosion, and processing technique is easy, Be widely used in Anchor Agent field, the cross-linked structure that it has make Anchor Agent be heated and stress under have relatively Good mechanical property and dimensional stability, and electrical property, chemical resistance are excellent, processing technique is easy and low price, but This cross-linked structure there is poor rigidity, wellability and the big defect of shrinkage factor so as to application is extremely limited it would be highly desirable to solve.
Content of the invention
The technical problem being existed based on background technology, the present invention proposes a kind of unsaturated polyester (UP) tree for Anchor Agent Fat, rigidity is good, and wellability is good, and shrinkage factor is little.
A kind of unsaturated polyester resin for Anchor Agent proposed by the present invention, its raw material includes by weight: methene fourth Diacid 20-35 part, M-phthalic acid 2-10 part, rosin acid 10-19 part, acetic anhydride 15-22 part, dipropylene glycol 15-25 part, second two Alcohol 8-16 part, diethylene glycol 10-30 part, fumaric acid 25-45 part, vinyltoluene 18-28 part, modified castor oil 1-3 part, it is situated between Porous molecular sieve 2-6 part, aerosil 1-4 part, butyl trimethoxy silane 0.5-1.5 part.
Preferably, modified castor oil adopts following technique preparation: sodium polyacrylate, water mixing and stirring add second Alcohol, 1,3- dipropylene glycol mixing and stirring obtain modified polyacrylate sodium；Oleum Ricini is vacuum dried, removes vacuum, cool down, Add di-2-ethylhexylphosphine oxide (4- phenyl isocyanate) under stirring, continue stirring, heat up, add modified polyacrylate sodium to continue to stir Mix, continue stirring under evacuation state, be down to room temperature and obtain modified castor oil.
Preferably, modified castor oil adopts following technique preparation: by sodium polyacrylate, water mixing and stirring, stirring temperature Spend for 65-75 DEG C, add ethanol, 1,3- dipropylene glycol mixing and stirring, whipping temp is 80-88 DEG C, obtain modified poly- third Olefin(e) acid sodium；Oleum Ricini is vacuum dried 50-80min, baking temperature is 125-135 DEG C, removes vacuum, be cooled to 65-78 DEG C, stir Mix and add di-2-ethylhexylphosphine oxide (4- phenyl isocyanate) under state, continue stirring 30-80min, be warming up to 80-88 DEG C, add modified Sodium polyacrylate continues stirring 30-60min, continues stirring 10-30min, be down to room temperature and obtain modified castor under evacuation state Oil.
Preferably, modified castor oil adopts following technique preparation: by weight by 0.5-2.5 part sodium polyacrylate, 40-60 Part water mixing and stirring, whipping temp is 65-75 DEG C, adds 2-4 part ethanol, 1-3 part 1, and 3- dipropylene glycol mix and blend is equal Even, whipping temp is 80-88 DEG C, obtains modified polyacrylate sodium；By weight 20-40 part Oleum Ricini is vacuum dried 50- 80min, baking temperature is 125-135 DEG C, removes vacuum, is cooled to 65-78 DEG C, adds 1-3 part di-2-ethylhexylphosphine oxide under stirring (4- phenyl isocyanate), continues stirring 30-80min, is warming up to 80-88 DEG C, adds 2-9 part modified polyacrylate sodium to continue to stir Mix 30-60min, continue stirring 10-30min under evacuation state, be down to room temperature and obtain modified castor oil.
Preferably, the weight of methylene succinic acid, M-phthalic acid, rosin acid, acetic anhydride, dipropylene glycol, ethylene glycol, diethylene glycol Amount ratio is 25-30:4-8:12-16:18-20:18-22:10-14:15-25.
Preferably, modified castor oil, mesopore molecular sieve, aerosil, the weight ratio of butyl trimethoxy silane are 1.5-2.5:3-5:2-3:0.8-1.2.
Preferably, its raw material includes by weight: methylene succinic acid 25-30 part, M-phthalic acid 4-8 part, rosin acid 12- 16 parts, acetic anhydride 18-20 part, dipropylene glycol 18-22 part, ethylene glycol 10-14 part, diethylene glycol 15-25 part, fumaric acid 30- 40 parts, vinyltoluene 20-26 part, modified castor oil 1.5-2.5 part, mesopore molecular sieve 3-5 part, aerosil 2-3 part, Butyl trimethoxy silane 0.8-1.2 part.
The present invention adopts conventional fabrication process to be obtained.
The present invention adopts methylene succinic acid, M-phthalic acid, rosin acid, acetic anhydride, dipropylene glycol, ethylene glycol, diethylene glycol Cooperate, make the viscosity of the present invention and wellability good；And mesopore molecular sieve not only can effectively reduce vinyltoluene volatile quantity, Improve the viscosity of the present invention and thixotropy further, and shrink of product rate reduces, can effectively ensure that external shape moreover it is possible in butyl Act on modified castor oil in the presence of trimethoxy silane, improve the mutual compatibility, further enhance wellability of the present invention Can, and mutual adhesion is fabulous, makes the rigidity of the present invention good.
In the modified castor oil of the present invention, Oleum Ricini is acted on di-2-ethylhexylphosphine oxide (4- phenyl isocyanate) after pretreatment The urethane that formed is covalently cross-linked, and in modified polyacrylate sodium, the mutual compatibility is fabulous, products therefrom toughness and hydrophobicity Good；And in modified polyacrylate sodium, sodium polyacrylate, ethanol, the effect of 1,3- dipropylene glycol formed unordered pile up cellular, big point Subchain is entangled with one another, and mechanical property is good, and specific surface area is big, and wellability is good, and the compatibility is good and unclassified stores between.
Specific embodiment
Below, by specific embodiment, technical scheme is described in detail.
Embodiment 1
A kind of unsaturated polyester resin for Anchor Agent proposed by the present invention, its raw material includes by weight: methene fourth 20 parts of diacid, 10 parts of M-phthalic acid, 10 parts of rosin acid, 22 parts of acetic anhydride, 15 parts of dipropylene glycol, 16 parts of ethylene glycol, diethylene glycol 10 parts, 45 parts of fumaric acid, 18 parts of vinyltoluene, 3 parts of modified castor oil, 2 parts of mesopore molecular sieve, aerosil 4 Part, 0.5 part of butyl trimethoxy silane.
Embodiment 2
A kind of unsaturated polyester resin for Anchor Agent proposed by the present invention, its raw material includes by weight: methene fourth 35 parts of diacid, 2 parts of M-phthalic acid, 19 parts of rosin acid, 15 parts of acetic anhydride, 25 parts of dipropylene glycol, 8 parts of ethylene glycol, diethylene glycol 30 Part, 25 parts of fumaric acid, 28 parts of vinyltoluene, 1 part of modified castor oil, 6 parts of mesopore molecular sieve, 1 part of aerosil, 1.5 parts of butyl trimethoxy silane.
Modified castor oil adopts the preparation of following technique: by sodium polyacrylate, water mixing and stirring, add ethanol, 1,3- Dipropylene glycol mixing and stirring obtains modified polyacrylate sodium；Oleum Ricini is vacuum dried, removes vacuum, cooling, stir shape Add di-2-ethylhexylphosphine oxide (4- phenyl isocyanate) under state, continue stirring, heat up, add modified polyacrylate sodium to continue stirring, take out Continue stirring under vacuum state, be down to room temperature and obtain modified castor oil.
Embodiment 3
A kind of unsaturated polyester resin for Anchor Agent proposed by the present invention, its raw material includes by weight: methene fourth 25 parts of diacid, 8 parts of M-phthalic acid, 12 parts of rosin acid, 20 parts of acetic anhydride, 18 parts of dipropylene glycol, 14 parts of ethylene glycol, diethylene glycol 15 Part, 40 parts of fumaric acid, 20 parts of vinyltoluene, 2.5 parts of modified castor oil, 3 parts of mesopore molecular sieve, aerosil 3 Part, 0.8 part of butyl trimethoxy silane.
Modified castor oil adopts following technique preparation: by weight will be equal to 2.5 parts of sodium polyacrylate, 40 parts of water mix and blends Even, whipping temp is 75 DEG C, adds 2 parts of ethanol, 3 parts of 1,3- dipropylene glycol mixing and stirring, and whipping temp is 80 DEG C, obtains Modified polyacrylate sodium；By weight 40 parts of Oleum Ricini are vacuum dried 50min, baking temperature is 135 DEG C, remove vacuum, cold But to 65 DEG C, under stirring, add 3 parts of di-2-ethylhexylphosphine oxides (4- phenyl isocyanate), continue stirring 30min, be warming up to 88 DEG C, Add 2 parts of modified polyacrylate sodium to continue stirring 60min, continue stirring 10min under evacuation state, be down to room temperature and obtain modification Oleum Ricini.
Embodiment 4
A kind of unsaturated polyester resin for Anchor Agent proposed by the present invention, its raw material includes by weight: methene fourth 30 parts of diacid, 4 parts of M-phthalic acid, 16 parts of rosin acid, 18 parts of acetic anhydride, 22 parts of dipropylene glycol, 10 parts of ethylene glycol, diethylene glycol 25 Part, 30 parts of fumaric acid, 26 parts of vinyltoluene, 1.5 parts of modified castor oil, 5 parts of mesopore molecular sieve, aerosil 2 Part, 1.2 parts of butyl trimethoxy silane.
Modified castor oil adopts following technique preparation: by weight will be equal to 0.5 part of sodium polyacrylate, 60 parts of water mix and blends Even, whipping temp is 65 DEG C, adds 4 parts of ethanol, 1 part of 1,3- dipropylene glycol mixing and stirring, and whipping temp is 88 DEG C, obtains Modified polyacrylate sodium；By weight 20 parts of Oleum Ricini are vacuum dried 80min, baking temperature is 125 DEG C, remove vacuum, cold But to 78 DEG C, under stirring, add 1 part of di-2-ethylhexylphosphine oxide (4- phenyl isocyanate), continue stirring 80min, be warming up to 80 DEG C, Add 9 parts of modified polyacrylate sodium to continue stirring 30min, continue stirring 30min under evacuation state, be down to room temperature and obtain modification Oleum Ricini.
Embodiment 5
A kind of unsaturated polyester resin for Anchor Agent proposed by the present invention, its raw material includes by weight: methene fourth 28 parts of diacid, 6 parts of M-phthalic acid, 14 parts of rosin acid, 19 parts of acetic anhydride, 20 parts of dipropylene glycol, 12 parts of ethylene glycol, diethylene glycol 20 Part, 35 parts of fumaric acid, 23 parts of vinyltoluene, 2 parts of modified castor oil, 4 parts of mesopore molecular sieve, aerosil 2.5 Part, 1 part of butyl trimethoxy silane.
Modified castor oil adopts following technique preparation: by sodium polyacrylate, water mixing and stirring, whipping temp is 70 DEG C, add ethanol, 1,3- dipropylene glycol mixing and stirring, whipping temp is 84 DEG C, obtains modified polyacrylate sodium；By Semen Ricini Oil vacuum drying 65min, baking temperature is 130 DEG C, removes vacuum, be cooled to 70 DEG C, adds di-2-ethylhexylphosphine oxide (4- under stirring Phenyl isocyanate), continue stirring 55min, be warming up to 84 DEG C, add modified polyacrylate sodium to continue stirring 45min, evacuation Continue stirring 20min under state, be down to room temperature and obtain modified castor oil.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto, Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its Inventive concept equivalent or change in addition, all should be included within the scope of the present invention.

Claims (7)

1. a kind of unsaturated polyester resin for Anchor Agent is it is characterised in that its raw material includes by weight: methylene succinic acid 20-35 part, M-phthalic acid 2-10 part, rosin acid 10-19 part, acetic anhydride 15-22 part, dipropylene glycol 15-25 part, ethylene glycol 8- 16 parts, diethylene glycol 10-30 part, fumaric acid 25-45 part, vinyltoluene 18-28 part, modified castor oil 1-3 part, mesoporous point Son sieve 2-6 part, aerosil 1-4 part, butyl trimethoxy silane 0.5-1.5 part.
2. it is used for the unsaturated polyester resin of Anchor Agent according to claim 1 it is characterised in that modified castor oil is using such as Lower technique preparation: sodium polyacrylate, water mixing and stirring add ethanol, 1,3- dipropylene glycol mixing and stirring to obtain Modified polyacrylate sodium；Oleum Ricini is vacuum dried, removes vacuum, cooling, (4- phenyl is different to add di-2-ethylhexylphosphine oxide under stirring Cyanate), continue stirring, heat up, add modified polyacrylate sodium to continue stirring, continue stirring under evacuation state, be down to room Temperature obtains modified castor oil.
3. the unsaturated polyester resin for Anchor Agent according to claim 1 or claim 2 is it is characterised in that modified castor oil is adopted With the preparation of following technique: by sodium polyacrylate, water mixing and stirring, whipping temp is 65-75 DEG C, adds ethanol, 1,3- bis- Mixed with propylene glycol stirs, and whipping temp is 80-88 DEG C, obtains modified polyacrylate sodium；Oleum Ricini is vacuum dried 50- 80min, baking temperature is 125-135 DEG C, removes vacuum, is cooled to 65-78 DEG C, adds di-2-ethylhexylphosphine oxide (4- benzene under stirring Based isocyanate), continue stirring 30-80min, be warming up to 80-88 DEG C, add modified polyacrylate sodium to continue stirring 30- 60min, continues stirring 10-30min, is down to room temperature and obtains modified castor oil under evacuation state.
4. it is used for the unsaturated polyester resin of Anchor Agent according to any one of claim 1-3 it is characterised in that modified castor Oil is using following technique preparation: by weight by 0.5-2.5 part sodium polyacrylate, 40-60 part water mixing and stirring, stirring temperature Spend for 65-75 DEG C, add 2-4 part ethanol, 1-3 part 1,3- dipropylene glycol mixing and stirring, whipping temp is 80-88 DEG C, obtains To modified polyacrylate sodium；By weight 20-40 part Oleum Ricini is vacuum dried 50-80min, baking temperature is 125-135 DEG C, Remove vacuum, be cooled to 65-78 DEG C, under stirring, add 1-3 part di-2-ethylhexylphosphine oxide (4- phenyl isocyanate), continue stirring 30-80min, is warming up to 80-88 DEG C, adds 2-9 part modified polyacrylate sodium to continue stirring 30-60min, continues under evacuation state Continuous stirring 10-30min, is down to room temperature and obtains modified castor oil.
5. it is used for the unsaturated polyester resin of Anchor Agent according to any one of claim 1-4 it is characterised in that methene fourth two Acid, M-phthalic acid, rosin acid, acetic anhydride, dipropylene glycol, ethylene glycol, the weight of diethylene glycol are than for 25-30:4-8:12-16: 18-20:18-22:10-14:15-25.
6. it is used for the unsaturated polyester resin of Anchor Agent according to any one of claim 1-5 it is characterised in that modified castor Oil, mesopore molecular sieve, aerosil, the weight of butyl trimethoxy silane are than for 1.5-2.5:3-5:2-3:0.8-1.2.
7. it is used for the unsaturated polyester resin of Anchor Agent according to any one of claim 1-6 it is characterised in that its raw material is pressed Weight portion includes: methylene succinic acid 25-30 part, M-phthalic acid 4-8 part, rosin acid 12-16 part, acetic anhydride 18-20 part, dipropyl Glycol 18-22 part, ethylene glycol 10-14 part, diethylene glycol 15-25 part, fumaric acid 30-40 part, vinyltoluene 20-26 part, Modified castor oil 1.5-2.5 part, mesopore molecular sieve 3-5 part, aerosil 2-3 part, butyl trimethoxy silane 0.8-1.2 Part.
CN201610743502.2A 2016-08-27 2016-08-27 Unsaturated polyester resin for anchoring agents Pending CN106366601A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610743502.2A CN106366601A (en) 2016-08-27 2016-08-27 Unsaturated polyester resin for anchoring agents

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Application Number Priority Date Filing Date Title
CN201610743502.2A CN106366601A (en) 2016-08-27 2016-08-27 Unsaturated polyester resin for anchoring agents

Publications (1)

Publication Number Publication Date
CN106366601A true CN106366601A (en) 2017-02-01

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Country Status (1)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102212172A (en) * 2011-02-17 2011-10-12 安徽淮河化工股份有限公司 Resin special for anchoring agent and preparation method thereof
CN102268167A (en) * 2010-12-25 2011-12-07 河南科技大学 Preparation method of low styrene volatile unsaturated polyester resin composite material
CN102558525A (en) * 2011-12-29 2012-07-11 安徽淮河化工股份有限公司 Method for preparing unsaturated polyester resin containing thixotropic agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268167A (en) * 2010-12-25 2011-12-07 河南科技大学 Preparation method of low styrene volatile unsaturated polyester resin composite material
CN102212172A (en) * 2011-02-17 2011-10-12 安徽淮河化工股份有限公司 Resin special for anchoring agent and preparation method thereof
CN102558525A (en) * 2011-12-29 2012-07-11 安徽淮河化工股份有限公司 Method for preparing unsaturated polyester resin containing thixotropic agent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
(英)菲利普·摩根等: "《玻璃增强塑料》", 28 February 1965, 中国工业出版社 *
周菊兴等: "《不饱和聚酯树脂》", 31 July 1985, 中国建筑工业出版社 *

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