CN106832155A - A kind of modified unsaturated polyester resin for improving heat resistance and preparation method thereof - Google Patents
A kind of modified unsaturated polyester resin for improving heat resistance and preparation method thereof Download PDFInfo
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- CN106832155A CN106832155A CN201710026657.9A CN201710026657A CN106832155A CN 106832155 A CN106832155 A CN 106832155A CN 201710026657 A CN201710026657 A CN 201710026657A CN 106832155 A CN106832155 A CN 106832155A
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- unsaturated polyester
- polyester resin
- heat resistance
- preparation
- modified unsaturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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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)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention provides a kind of modified unsaturated polyester resin for improving heat resistance and preparation method thereof, epoxy curing agent and unsaturated polyester resin solidifying agent are added after appropriate GMA, epoxy resin and unsaturated polyester resin are sufficiently mixed, stirred, vacuumized curing molding by taking-up bubble.The advantage of the invention is that epoxide group and the double bond success by GMA are incorporated into epoxy resin in unsaturated polyester resin, crosslinked polymer network is formed.It is also an advantage of the present invention that control reaction speed and reaction sequence, are achieved by controlling the temperature and time of curing reaction.Cross-linked polymer initial decomposition temperature, decomposition mechanism temperature and tensile strength are lifted substantially more before modified, effectively improve the heat resistance of unsaturated polyester resin.
Description
Technical field
It is modified field, more particularly to a kind of GMA and asphalt mixtures modified by epoxy resin the invention belongs to unsaturated polyester resin
The method of the common modified unsaturated polyester resin of fat.
Background technology
Unsaturated polyester resin (UPR) is obtained by binary acid, dihydroxylic alcohols through polycondensation reaction, is the main product of thermosetting resin
One of kind.Because it has preferable production technology, mechanical property and electrical property, at the same it is cheap, in agricultural, traffic, build
Build, the aspect such as automobile, electronic apparatus and national defense industry is widely used.But toughness is poor, surface is easy because unsaturated polyester (UP) is present
The shortcomings of cracking, poor fire and larger product molding shrinkage factor, the poor problem of hot property is especially in the presence of, so as to limit
Its range of application.The material prepared using the method for modifying of current unsaturated polyester resin is susceptible to be separated, and its performance is special
It is not that heat resistance can not meet increasingly harsher use requirement.To expand application field, wanting for some special dimensions is met
Ask, it is necessary to optimize method of modifying.
The content of the invention
The purpose of the present invention：For the problem of current unsaturated polyester resin hot property difference, there is provided a kind of methacrylic acid
Polyglycidyl and the common modified unsaturated polyester resin of epoxy resin are come the method that improves unsaturated polyester resin heat resistance.
Technical scheme：Unsaturated polyester resin is entered with GMA and epoxy resin ingredient
Row is modified, and adds epoxy curing agent and unsaturated polyester resin solidifying agent, and being made one by modifying ingredients ratio is
The modified unsaturated polyester resin of row.Described modified unsaturated polyester resin is according to mass fraction meter, each component content：No
100 parts of saturated polyester resin, 5~25 parts of epoxy resin, 0.5~2.5 part of GMA, epoxy curing agent
3~15 parts, 3~5 parts of cyclohexanone peroxide-cobalt naphthenate.The preparation method of this modified unsaturated polyester resin includes：
(1) GMA, epoxy resin and unsaturated polyester (UP) are weighed in flask, mechanical agitation 30min,
Weigh epoxy curing agent to be added in flask, use mechanical agitation 10min, be eventually adding unsaturated polyester resin solidifying agent and arrive
In flask, the mixture in flask is poured into beaker after stirring 1min, above rotating speed is 500~600r/min；
Preferably, described epoxy resin is E51.
Preferably, described epoxy curing agent is methyl tetrahydrophthalic anhydride, described unsaturated polyester (UP)
Resin curing agent is cyclohexanone peroxide-cobalt naphthenate system.
Preferably, described rotating speed is 550~580r/min.
(2) material in beaker is put into vacuum drying oven, bubble therein is removed by the method for vacuumizing；
(3) being poured into Teflon mould by vacuumizing the mixture of bubble removing, 2 are solidified at normal temperatures small
When, then solidify under the conditions of 150 DEG C 6~10 hours and be molded.
Preferably, under the conditions of described 150 DEG C hardening time be 8 hours, ambient temperature curing is first to allow unsaturated double-bond
React, solidification is to allow epoxide group to react under the conditions of 150 DEG C.
Technique effect of the invention：Double bond in GMA can be with the double bond in unsaturated polyester (UP) normal
Temperature is lower to there is curing reaction, while the epoxide group contained in GMA under 150 DEG C of condition high temperature can
It is combined together with epoxy resin well by open loop, forms crosslinked polymer network.The handle by way of chemical bond is connected
Epoxy resin has been incorporated into unsaturated polyester (UP), force it is compatible so that be separated reduce, so as to enhance unsaturated polyester resin
Performance.It is also an advantage of the present invention that control reaction speed and reaction sequence, by the temperature and time for controlling curing reaction
It is achieved.The normal temperature cure time is particularly controlled for 2 hours, normal temperature cure deficiency of time or long and influence reaction is prevented
As a result, properties of product are finally influenceed；Direct high temperature is also prevented from so that curing reaction is uncontrollable and influences properties of product.Crosslinking is poly-
Compound initial decomposition temperature, decomposition mechanism temperature and tensile strength are lifted substantially more before modified.
Brief description of the drawings
Fig. 1 is embodiment 2 by the infrared spectrum after the curable unsaturated polyester being modified.Can from infrared spectrogram
Arrive, in 914cm-1The infrared absorption peak of the epoxide group at place has been disappeared, and this shows epoxy resin and glycidyl
Propyl ester has occurred that reaction.While 1645cm-1The infrared absorption peak of the carbon-carbon double bond at place is also disappeared, it was demonstrated that methacrylic acid
Polyglycidyl there occurs reaction with unsaturated polyester (UP), and this just illustrates epoxy resin by anti-with GMA
In should having been introduced into unsaturated polyester (UP) system.
Specific embodiment
Embodiment 1：
(1) 24g unsaturated polyester (UP)s, 1.2g epoxy resin and 0.12g GMAs are first weighed in three mouthfuls of burnings
In bottle, mechanical agitation 0.5h is used, after stirring, add 0.864g methyl tetrahydrophthalic anhydrides (MTHPA), mechanical agitation
10min, is eventually adding 0.6g cyclohexanone peroxides-cobalt naphthenate system curing agent, after stirring 1min, pours into beaker, rotating speed
It is 550r/min；
(2) mixture for stirring is put into vacuum drying oven, the bubble in mixture is removed by vacuumizing, such as
Fruit once vacuumizes the bubble that could not be removed completely in mixture, can be removed by repeatedly vacuumizing；
(3) mixture for having removed bubble is poured into Teflon mould, elder generation is solid at normal temperatures in being put into baking oven
Change 2h, 150 DEG C of solidification 8h shapings are then warmed up to again.
Embodiment 2：
(1) 24g unsaturated polyester (UP)s, 2.4g epoxy resin and 0.24g GMAs are first weighed in three mouthfuls of burnings
In bottle, mechanical agitation 0.5h is used, after stirring, add 1.728g methyl tetrahydrophthalic anhydrides (MTHPA), mechanical agitation
10min, is eventually adding 0.6g cyclohexanone peroxides-cobalt naphthenate system curing agent, after stirring 1min, pours into beaker, rotating speed
It is 550r/min；
(2) mixture for stirring is put into vacuum drying oven, the bubble in mixture is removed by vacuumizing, such as
Fruit once vacuumizes the bubble that could not be removed completely in mixture, can be removed by repeatedly vacuumizing；
(3) mixture for having removed bubble is poured into Teflon mould, elder generation is solid at normal temperatures in being put into baking oven
Change 2h, 150 DEG C of solidification 8h shapings are then warmed up to again.
Embodiment 3：
(1) 24g unsaturated polyester (UP)s, 3.6g epoxy resin and 0.36g GMAs are first weighed in three mouthfuls of burnings
In bottle, mechanical agitation 0.5h is used, after stirring, add 2.592g methyl tetrahydrophthalic anhydrides (MTHPA), mechanical agitation
10min, is eventually adding 0.6g cyclohexanone peroxides-cobalt naphthenate system curing agent, after stirring 1min, pours into beaker, rotating speed
It is 550r/min；
(2) mixture for stirring is put into vacuum drying oven, the bubble in mixture is removed by vacuumizing；
(3) mixture for having removed bubble is poured into Teflon mould, elder generation is solid at normal temperatures in being put into baking oven
Change 2h, 150 DEG C of solidification 8h shapings are then warmed up to again.
Embodiment 4：
(1) 24g unsaturated polyester (UP)s, 4.8g epoxy resin and 0.48g GMAs are first weighed in three mouthfuls of burnings
In bottle, mechanical agitation 0.5h is used, after stirring, add 3.456g methyl tetrahydrophthalic anhydrides (MTHPA), mechanical agitation
10min, is eventually adding 0.6g cyclohexanone peroxides-cobalt naphthenate system curing agent, after stirring 1min, pours into beaker, rotating speed
It is 550r/min；
(2) mixture for stirring is put into vacuum drying oven, the bubble in mixture is removed by vacuumizing；
(3) mixture for having removed bubble is poured into Teflon mould, elder generation is solid at normal temperatures in being put into baking oven
Change 2h, 150 DEG C of solidification 8h shapings are then warmed up to again.
Comparative example 1：
Without epoxy resin, remaining material addition and operating procedure are with embodiment 1.
Comparative example 2：
Without GMA, remaining material addition and operating procedure are with embodiment 1.
Table 1 is the Thermogravimetric Data of embodiment 1-4, comparative example 1-2 and unsaturated polyester (UP).As it can be seen from table 1 using first
The heat resistance of the unsaturated polyester (UP) of base Glycidyl Acrylate and epoxy resin modification has substantially compared to unsaturated polyester (UP)
Raising.The temperature of initial decomposition of modified unsaturated polyester (UP) has brought up to 289~334 DEG C from 255 DEG C, most fast decomposition rate
Temperature also brought up to 400~414 DEG C from 395 DEG C.
Table 2 is unsaturated polyester modified front and rear tensile strength and elongation at break data.From table 2 it can be seen that modified
The tensile strength of unsaturated polyester (UP) afterwards is obviously improved, while elongation at break change is little.
The Thermogravimetric Data of the embodiment 1-4 of table 1, comparative example 1-2 and unsaturated polyester (UP)
| Initial decomposition temperature/DEG C | Decomposition mechanism temperature/DEG C | |
| Embodiment 1 | 289 | 400 |
| Embodiment 2 | 324 | 406 |
| Embodiment 3 | 330 | 410 |
| Embodiment 4 | 334 | 414 |
| Comparative example 1 | 257 | 396 |
| Comparative example 2 | 259 | 398 |
| Unsaturated polyester (UP) | 255 | 395 |
Tensile strength and elongation at break data before and after table 2 is unsaturated polyester modified
Claims (6)
1. it is a kind of improve heat resistance modified unsaturated polyester resin, it is characterised in that described modified unsaturated polyester tree
Fat is according to mass fraction meter, each component content：100 parts of unsaturated polyester resin, 5~25 parts of epoxy resin, methacrylic acid
0.5~2.5 part of polyglycidyl, 3~15 parts of epoxy curing agent, 3~5 parts of cyclohexanone peroxide-cobalt naphthenate.
2. it is a kind of it is as claimed in claim 1 improve heat resistance modified unsaturated polyester resin preparation method, its feature
It is that described preparation method includes：
(1) GMA, epoxy resin and unsaturated polyester (UP) are weighed in flask, mechanical agitation 30min is weighed
Epoxy curing agent is added in flask, uses mechanical agitation 10min, is eventually adding unsaturated polyester resin solidifying agent to flask
In, the mixture in flask is poured into beaker after stirring 1min, above rotating speed is 500~600r/min；
(2) material in beaker is put into vacuum drying oven, bubble therein is removed by the method for vacuumizing；
(3) being poured into Teflon mould by vacuumizing the mixture of bubble removing, at normal temperatures solidify 2 hours, so
Solidify under the conditions of 150 DEG C afterwards 6~10 hours and be molded.
3. the preparation method of the modified unsaturated polyester resin of heat resistance is improved as claimed in claim 2, it is characterised in that
Epoxy resin described in step (1) is E51.
4. the preparation method of the modified unsaturated polyester resin of heat resistance is improved as claimed in claim 2, it is characterised in that
Epoxy curing agent described in step (1) is methyl tetrahydrophthalic anhydride, described unsaturated polyester resin solidifying agent
It is cyclohexanone peroxide-cobalt naphthenate system.
5. the preparation method of the modified unsaturated polyester resin of heat resistance is improved as claimed in claim 2, it is characterised in that
Rotating speed described in step (1) is 550~580r/min.
6. the preparation method of the modified unsaturated polyester resin of heat resistance is improved as claimed in claim 2, it is characterised in that
Hardening time is 8 hours under the conditions of 150 DEG C described in step (3).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710026657.9A CN106832155B (en) | 2017-01-14 | 2017-01-14 | A kind of modified unsaturated polyester resin and preparation method thereof improving heat resistance |
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| CN201710026657.9A CN106832155B (en) | 2017-01-14 | 2017-01-14 | A kind of modified unsaturated polyester resin and preparation method thereof improving heat resistance |
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| CN106832155B CN106832155B (en) | 2018-12-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109049460A (en) * | 2018-07-09 | 2018-12-21 | 张家港市德仁科教仪器设备有限公司 | A kind of liver cast sample embedding method and model |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4931787A (en) * | 1972-05-25 | 1974-03-22 | ||
| CN103183945A (en) * | 2011-12-28 | 2013-07-03 | 上海贝诺装饰新材料有限公司 | Modified unsaturated polyester resin and preparation method thereof |
-
2017
- 2017-01-14 CN CN201710026657.9A patent/CN106832155B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4931787A (en) * | 1972-05-25 | 1974-03-22 | ||
| CN103183945A (en) * | 2011-12-28 | 2013-07-03 | 上海贝诺装饰新材料有限公司 | Modified unsaturated polyester resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109049460A (en) * | 2018-07-09 | 2018-12-21 | 张家港市德仁科教仪器设备有限公司 | A kind of liver cast sample embedding method and model |
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| Publication number | Publication date |
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| CN106832155B (en) | 2018-12-07 |
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