CN109957096A - A kind of pultrusion unsaturated-resin and preparation process - Google Patents
A kind of pultrusion unsaturated-resin and preparation process Download PDFInfo
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- CN109957096A CN109957096A CN201711414032.6A CN201711414032A CN109957096A CN 109957096 A CN109957096 A CN 109957096A CN 201711414032 A CN201711414032 A CN 201711414032A CN 109957096 A CN109957096 A CN 109957096A
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- resin
- pultrusion
- unsaturated
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- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- 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
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
The invention discloses a kind of pultrusion unsaturated-resin and preparation processes, the resin is made of raw material from the following weight: 4000~6000 parts of phthalic anhydride, 600~1200 parts of propylene glycol, 1500~1800 parts of ethylene glycol, 1600~2000 parts of neopentyl glycol, 800~1000 parts of cis-butenedioic anhydride, 2~6 parts of polymerization inhibitor, 1~5 part of antioxidant, 0.1~0.8 part of diluent.Pultrusion unsaturated-resin of the present invention is under the premise of meeting pultrude process rapid shaping, with better heat resistance, thermal change temperature is up to 98 DEG C or more, the mechanical properties such as toughness and intensity are significantly increased simultaneously, pultrusion of the maximum pressure up to 1780N, especially suitable for complex shapes and high strength sectional material.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of pultrusion unsaturated-resin and preparation process.
Background technique
Pultrude process is a kind of method of linear profile of continuous production FRP, this method be under the drive of traction device, with
Resin is Matrix adhesive, and non-twist glass-fiber-fabric or other reinforcing materials are impregnated, is preforming, then passes through the molding that is heating and curing.
The profile of the various section configurations of production, such as pipe, stick, entity or hollow profile surface is smooth, dimensional accuracy is high, and with good
Good corrosion resistance and electrical insulating property, it is more and more extensive to be applied to the every field such as national defence, industry, civilian.
Currently, the resin matrix of pultrusion composite materials is mainly unsaturated-resin and epoxy resin, chemical characteristic and solid
Mechanical performance after change significantly affects technology difficulty and product quality, wherein applying at most is unsaturated-resin, accounts for about drawing
The 85%~90% of extruding process amount of resin, the resin are good to the wellability of fiber, and cure shrinkage is smaller, are especially advantageous for technique
Progress, but in terms of existing defects after heat resistance and solidification are unable to satisfy its work in quality
Skill requirement.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of pultrusion unsaturated-resin and preparation processes, to solve
The technical issues of existing resin is unable to satisfy pultrusion molding process.
To realize the above technical purpose, the invention adopts the following technical scheme:
A kind of pultrusion unsaturated-resin, is made of raw material from the following weight: 4000~6000 parts of phthalic anhydride, propylene glycol 600~
1200 parts, 1500~1800 parts of ethylene glycol, 1600~2000 parts of neopentyl glycol, 800~1000 parts of cis-butenedioic anhydride, 2~6 parts of polymerization inhibitor,
1~5 part of antioxidant, 0.1~0.8 part of diluent.
Preferably, the polymerization inhibitor is p-tert-Butylcatechol.
Preferably, the antioxidant is triphenyl phosphite.
Preferably, the diluent is acetone or alcohol.
The preparation process of above-mentioned pultrusion unsaturated-resin, comprising the following steps:
1) phthalic anhydride, propylene glycol, ethylene glycol, neopentyl glycol, cis-butenedioic anhydride investment dimerization pot are stirred, mixing time is 1.5~2h；
2) mixture in dimerization pot is warming up to 105~110 DEG C, after moisture distillation, continues to be warming up to 205~210 DEG C, heat preservation
3~5h；
3) it after polymerization inhibitor and antioxidant being added in above-mentioned mixture, is vacuumized, vacuum degree must not be lower than -0.08MPa, very
The empty time is 2~3 h；
4) when above-mentioned mixture being cooled to 60~80 DEG C, diluent thinning is added, obtain after thinning acid value be 40~
The unsaturated-resin of 45mgHOK/g.
Pultrusion unsaturated-resin of the present invention has preferably heat-resisting under the premise of meeting pultrude process rapid shaping
Property, thermal change temperature is up to 98 DEG C or more, while the mechanical properties such as toughness and intensity are significantly increased, and greatest compressive strength is reachable
1780N, the pultrusion especially suitable for complex shapes and high strength sectional material.
Specific embodiment
The present invention is further illustrated below by way of specific embodiment.But the detail of embodiment is only used for explaining this hair
It is bright, it should not be construed as the limitation of the technical solution total to the present invention.
Embodiment 1
A kind of pultrusion unsaturated-resin, is made of raw material from the following weight: 4000 parts of phthalic anhydride, 600 parts of propylene glycol, and ethylene glycol
1500 parts, 1600 parts of neopentyl glycol, 800 parts of cis-butenedioic anhydride, 2 parts of tert-butyl catechol, 1 part of triphenyl phosphite, 0.1 part of acetone.
The preparation process of above-mentioned pultrusion unsaturated-resin, comprising the following steps:
1) phthalic anhydride, propylene glycol, ethylene glycol, neopentyl glycol, cis-butenedioic anhydride investment dimerization pot are stirred, mixing time 1.5h；
2) mixture in dimerization pot is warming up to 105 DEG C, after moisture distillation, continues to be warming up to 205 DEG C, keeps the temperature 3h；
3) it after polymerization inhibitor and antioxidant being added in above-mentioned mixture, is vacuumized, vacuum degree is -0.09MPa, vacuum time
For 2 h；
4) when above-mentioned mixture being cooled to 60 DEG C, diluent thinning is added, the insatiable hunger that acid value is 40mgHOK/g is obtained after thinning
And resin.
Embodiment 2
A kind of pultrusion unsaturated-resin, is made of raw material from the following weight: 4500 parts of phthalic anhydride, 800 parts of propylene glycol, and ethylene glycol
1580 parts, 1700 parts of neopentyl glycol, 860 parts of cis-butenedioic anhydride, 4 parts of p-tert-Butylcatechol, 2 parts of triphenyl phosphite, acetone 0.3
Part.
The preparation process of above-mentioned pultrusion unsaturated-resin, comprising the following steps:
1) phthalic anhydride, propylene glycol, ethylene glycol, neopentyl glycol, cis-butenedioic anhydride investment dimerization pot are stirred, mixing time 1.8h；
2) mixture in dimerization pot is warming up to 108 DEG C, after moisture distillation, continues to be warming up to 207 DEG C, keeps the temperature 4h；
3) it after polymerization inhibitor and antioxidant being added in above-mentioned mixture, is vacuumized, vacuum degree is -0.095MPa, vacuum time
For 2.5h；
4) when above-mentioned mixture being cooled to 67 DEG C, diluent thinning is added, the insatiable hunger that acid value is 42mgHOK/g is obtained after thinning
And resin.
Embodiment 3
A kind of pultrusion unsaturated-resin, is made of raw material from the following weight: 5800 parts of phthalic anhydride, 950 parts of propylene glycol, and ethylene glycol
1600 parts, 1900 parts of neopentyl glycol, 980 parts of cis-butenedioic anhydride, 5 parts of p-tert-Butylcatechol, 5 parts of triphenyl phosphite, ethyl alcohol 0.6
Part.
The preparation process of above-mentioned pultrusion unsaturated-resin, comprising the following steps:
1) phthalic anhydride, propylene glycol, ethylene glycol, neopentyl glycol, cis-butenedioic anhydride investment dimerization pot are stirred, mixing time 2h；
2) mixture in dimerization pot is warming up to 110 DEG C, after moisture distillation, continues to be warming up to 210 DEG C, keeps the temperature 5h；
3) it after polymerization inhibitor and antioxidant being added in above-mentioned mixture, is vacuumized, vacuum degree is -0.1MPa, and vacuum time is
3 h；
4) when above-mentioned mixture being cooled to 80 DEG C, diluent thinning is added, the insatiable hunger that acid value is 45mgHOK/g is obtained after thinning
And resin.
Claims (5)
1. a kind of pultrusion unsaturated-resin, it is characterised in that be made of raw material from the following weight: 4000~6000 parts of phthalic anhydride,
600~1200 parts of propylene glycol, 1500~1800 parts of ethylene glycol, 1600~2000 parts of neopentyl glycol, 800~1000 parts of cis-butenedioic anhydride, resistance
2~6 parts of poly- agent, 1~5 part of antioxidant, 0.1~0.8 part of diluent.
2. pultrusion unsaturated-resin according to claim 1, it is characterised in that the polymerization inhibitor is to tert-butyl o
Benzenediol.
3. pultrusion unsaturated-resin according to claim 1, it is characterised in that the antioxidant is phosphorous triphenyl phosphate
Ester.
4. pultrusion unsaturated-resin according to claim 1, it is characterised in that the diluent is acetone or alcohol.
5. the preparation process of pultrusion unsaturated-resin according to claim 1, it is characterised in that the following steps are included:
1) phthalic anhydride, propylene glycol, ethylene glycol, neopentyl glycol, cis-butenedioic anhydride investment dimerization pot are stirred, mixing time is 1.5~2h；
2) mixture in dimerization pot is warming up to 105~110 DEG C, after moisture distillation, continues to be warming up to 205~210 DEG C, heat preservation
3~5h；
3) it after polymerization inhibitor and antioxidant being added in above-mentioned mixture, is vacuumized, vacuum degree must not be lower than -0.08MPa, very
The empty time is 2~3 h；
4) when above-mentioned mixture being cooled to 60~80 DEG C, diluent thinning is added, obtain after thinning acid value be 40~
The unsaturated-resin of 45mgHOK/g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711414032.6A CN109957096A (en) | 2017-12-25 | 2017-12-25 | A kind of pultrusion unsaturated-resin and preparation process |
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| CN201711414032.6A CN109957096A (en) | 2017-12-25 | 2017-12-25 | A kind of pultrusion unsaturated-resin and preparation process |
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Citations (11)
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|---|---|---|---|---|
| US5614299A (en) * | 1996-02-26 | 1997-03-25 | Kabushiki Kaisha Kobe Seiko Sho | Heat-resistant unsaturated polyester resin composition and heat-resistant fiber-reinforced composite material |
| CN1324373A (en) * | 1998-10-19 | 2001-11-28 | 戴尼亚化学有限公司 | Unsaturated polyester resins |
| CN101560293A (en) * | 2009-05-18 | 2009-10-21 | 上海新天和树脂有限公司 | Pultrusion unsaturated polyester resin prepared from bio-alcohol and preparation method thereof |
| CN101608007A (en) * | 2009-07-07 | 2009-12-23 | 温州市中侨树脂化工实业公司 | Fast pultrusion unsaturated polyester resin and preparation method thereof |
| CN102174178A (en) * | 2011-03-15 | 2011-09-07 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for pultrusion and preparation method thereof |
| CN102181017A (en) * | 2011-04-22 | 2011-09-14 | 常州华科树脂有限公司 | Unsaturated polyester resin for machine-made or hand-pasted plane skylight and preparation method thereof |
| CN103013304A (en) * | 2012-12-07 | 2013-04-03 | 武汉工程大学 | Method for preparation of water-based UV-curing unsaturated polyester by solvent azeotropy |
| CN103387661A (en) * | 2013-07-22 | 2013-11-13 | 南通天和树脂有限公司 | Phosphorus-series reaction-type flame-retardant unsaturated polyester resin |
| CN104650300A (en) * | 2015-01-31 | 2015-05-27 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for radome and method for preparing unsaturated polyester resin for radome |
| CN106916289A (en) * | 2015-12-24 | 2017-07-04 | 株洲时代电气绝缘有限责任公司 | A kind of low viscosity unsaturated-resin and preparation method thereof |
| CN107009649A (en) * | 2017-05-14 | 2017-08-04 | 南通德瑞森复合材料有限公司 | A kind of production technology of fiberglass drawing and extruding section bar |
-
2017
- 2017-12-25 CN CN201711414032.6A patent/CN109957096A/en active Pending
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| CN1324373A (en) * | 1998-10-19 | 2001-11-28 | 戴尼亚化学有限公司 | Unsaturated polyester resins |
| CN101560293A (en) * | 2009-05-18 | 2009-10-21 | 上海新天和树脂有限公司 | Pultrusion unsaturated polyester resin prepared from bio-alcohol and preparation method thereof |
| CN101608007A (en) * | 2009-07-07 | 2009-12-23 | 温州市中侨树脂化工实业公司 | Fast pultrusion unsaturated polyester resin and preparation method thereof |
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| CN103013304A (en) * | 2012-12-07 | 2013-04-03 | 武汉工程大学 | Method for preparation of water-based UV-curing unsaturated polyester by solvent azeotropy |
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| CN104650300A (en) * | 2015-01-31 | 2015-05-27 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for radome and method for preparing unsaturated polyester resin for radome |
| CN106916289A (en) * | 2015-12-24 | 2017-07-04 | 株洲时代电气绝缘有限责任公司 | A kind of low viscosity unsaturated-resin and preparation method thereof |
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Application publication date: 20190702 |
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