CN106832155B - A kind of modified unsaturated polyester resin and preparation method thereof improving heat resistance - Google Patents
A kind of modified unsaturated polyester resin and preparation method thereof improving heat resistance Download PDFInfo
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- CN106832155B CN106832155B CN201710026657.9A CN201710026657A CN106832155B CN 106832155 B CN106832155 B CN 106832155B CN 201710026657 A CN201710026657 A CN 201710026657A CN 106832155 B CN106832155 B CN 106832155B
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- unsaturated polyester
- polyester resin
- heat resistance
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- epoxy
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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 and preparation method thereof for improving heat resistance, epoxy curing agent and unsaturated polyester resin solidifying agent are added after appropriate glycidyl methacrylate, epoxy resin and unsaturated polyester resin are sufficiently mixed, stir evenly, vacuumize take out bubble can curing molding.The advantage of the invention is that epoxy group and the double bond success by glycidyl methacrylate are introduced 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, the temperature and time by controlling curing reaction is achieved.Cross-linked polymer initial decomposition temperature, decomposition mechanism temperature and tensile strength are promoted obviously more before modified, effectively improve the heat resistance of unsaturated polyester resin.
Description
Technical field
The invention belongs to the modified field of unsaturated polyester resin, in particular to a kind of glycidyl methacrylate and asphalt mixtures modified by epoxy resin
The method of the common modified unsaturated polyester resin of rouge.
Background technique
Unsaturated polyester resin (UPR) is made by binary acid, dihydric alcohol through polycondensation reaction, is the main product of thermosetting resin
One of kind.Because it is with preferable production technology, mechanical property and electrical property, at the same it is cheap, in agricultural, traffic, build
It builds, automobile, electronic apparatus and national defense industry etc. are widely used.But since that there are toughness is poor, surface is easy for unsaturated polyester (UP)
Cracking, the disadvantages of poor fire and product molding shrinking percentage are larger, are especially in the presence of the poor problem of hot property, to limit
Its application range.It is easy to happen using material prepared by the method for modifying of current unsaturated polyester resin and is mutually separated, performance is special
It is not that heat resistance is not able to satisfy increasingly harsher requirement.To expand application field, meet wanting for some special dimensions
It asks, it is necessary to optimize method of modifying.
Summary of the invention
The purpose of the present invention: for the problem of current unsaturated polyester resin hot property difference, a kind of methacrylic acid is provided
Polyglycidyl and the common modified unsaturated polyester resin of epoxy resin are come the method that improves unsaturated polyester resin heat resistance.
Technical solution of the present invention: with glycidyl methacrylate and epoxy resin ingredient to unsaturated polyester resin into
Row is modified, and epoxy curing agent and unsaturated polyester resin solidifying agent is added, and a system has been made by modifying ingredients ratio
Arrange modified unsaturated polyester resin.The modified unsaturated polyester resin is according to mass fraction meter, each component content are as follows: no
100 parts of saturated polyester resin, 5~25 parts of epoxy resin, 0.5~2.5 part of glycidyl methacrylate, 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) glycidyl methacrylate, epoxy resin and unsaturated polyester (UP) are weighed in flask, mechanical stirring 30min,
It weighs epoxy curing agent to be added in flask, with mechanical stirring 10min, is eventually adding unsaturated polyester resin solidifying agent and arrives
In flask, the mixture in flask is poured into beaker after stirring 1min, the above revolving speed is 500~600r/min；
Preferably, the epoxy resin is E51.
Preferably, the epoxy curing agent is methyl tetrahydrophthalic anhydride, the unsaturated polyester (UP)
Resin curing agent is cyclohexanone peroxide-cobalt naphthenate system.
Preferably, the revolving speed is 550~580r/min.
(2) material in beaker is put into vacuum drying oven, bubble therein is removed by the method vacuumized；
(3) mixture by vacuumizing bubble removing is poured into Teflon mould, it is small solidifies 2 at normal temperature
When, then solidify under the conditions of 150 DEG C 6~10 hours and forms.
Preferably, under the conditions of described 150 DEG C curing time be 8 hours, ambient temperature curing is first to allow unsaturated double-bond
It reacts, solidification is that epoxy group is allowed to react under the conditions of 150 DEG C.
Technical effect of the invention: the double bond in glycidyl methacrylate can be with the double bond in unsaturated polyester (UP) normal
Temperature is lower to occur curing reaction, while the epoxy group contained in glycidyl methacrylate under 150 DEG C of condition high temperature can
It is combined together well with epoxy resin by open loop, forms crosslinked polymer network.The handle by way of chemistry key connection
Epoxy resin has been introduced into unsaturated polyester (UP), forces compatible so that mutually separating reduction, 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.Especially control the normal temperature cure time be 2 hours, prevent the normal temperature cure time insufficient or it is too long and influence react
As a result, finally influencing properties of product；Being also prevented from direct high temperature makes curing reaction be unable to control and influence properties of product.Crosslinking is poly-
Object initial decomposition temperature, decomposition mechanism temperature and tensile strength is closed to be promoted more before modified obviously.
Detailed description of the invention
Fig. 1 is the infrared spectrum after the curable unsaturated polyester modified of embodiment 2.It can from infrared spectrogram
It arrives, in 914cm-1The infrared absorption peak of the epoxy group at place has disappeared, this shows epoxy resin and glycidyl
Propyl ester has occurred that reaction.1645cm simultaneously-1The infrared absorption peak of the carbon-carbon double bond at place also disappears, it was demonstrated that methacrylic acid
Polyglycidyl is reacted with unsaturated polyester (UP), and it is anti-with glycidyl methacrylate that this just illustrates that epoxy resin passes through
It should have been introduced into unsaturated polyester (UP) system.
Specific embodiment
Embodiment 1:
(1) 24g unsaturated polyester (UP), 1.2g epoxy resin and 0.12g glycidyl methacrylate is first weighed to burn in three mouthfuls
In bottle, it is added 0.864g methyl tetrahydrophthalic anhydride (MTHPA), mechanical stirring after mixing evenly with mechanical stirring 0.5h
10min is eventually adding 0.6g cyclohexanone peroxide-cobalt naphthenate system curing agent, after stirring 1min, pours into beaker, revolving speed
It is 550r/min；
(2) mixture stirred evenly 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 completely removed in mixture, can be removed by repeatedly vacuumizing；
(3) mixture for having removed bubble is poured into Teflon mould, is put into baking oven first solid at normal temperature
Change 2h, is then warming up to 150 DEG C of solidification 8h moldings again.
Embodiment 2:
(1) 24g unsaturated polyester (UP), 2.4g epoxy resin and 0.24g glycidyl methacrylate is first weighed to burn in three mouthfuls
In bottle, it is added 1.728g methyl tetrahydrophthalic anhydride (MTHPA), mechanical stirring after mixing evenly with mechanical stirring 0.5h
10min is eventually adding 0.6g cyclohexanone peroxide-cobalt naphthenate system curing agent, after stirring 1min, pours into beaker, revolving speed
It is 550r/min；
(2) mixture stirred evenly 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 completely removed in mixture, can be removed by repeatedly vacuumizing；
(3) mixture for having removed bubble is poured into Teflon mould, is put into baking oven first solid at normal temperature
Change 2h, is then warming up to 150 DEG C of solidification 8h moldings again.
Embodiment 3:
(1) 24g unsaturated polyester (UP), 3.6g epoxy resin and 0.36g glycidyl methacrylate is first weighed to burn in three mouthfuls
In bottle, it is added 2.592g methyl tetrahydrophthalic anhydride (MTHPA), mechanical stirring after mixing evenly with mechanical stirring 0.5h
10min is eventually adding 0.6g cyclohexanone peroxide-cobalt naphthenate system curing agent, after stirring 1min, pours into beaker, revolving speed
It is 550r/min；
(2) mixture stirred evenly 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, is put into baking oven first solid at normal temperature
Change 2h, is then warming up to 150 DEG C of solidification 8h moldings again.
Embodiment 4:
(1) 24g unsaturated polyester (UP), 4.8g epoxy resin and 0.48g glycidyl methacrylate is first weighed to burn in three mouthfuls
In bottle, it is added 3.456g methyl tetrahydrophthalic anhydride (MTHPA), mechanical stirring after mixing evenly with mechanical stirring 0.5h
10min is eventually adding 0.6g cyclohexanone peroxide-cobalt naphthenate system curing agent, after stirring 1min, pours into beaker, revolving speed
It is 550r/min；
(2) mixture stirred evenly 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, is put into baking oven first solid at normal temperature
Change 2h, is then warming up to 150 DEG C of solidification 8h moldings again.
Comparative example 1:
Epoxy resin is not added, remaining substance additive amount and operating procedure are the same as embodiment 1.
Comparative example 2:
Glycidyl methacrylate is not added, remaining substance additive amount and operating procedure are the same as 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 obviously compared to unsaturated polyester (UP)
Raising.The temperature of initial decomposition of modified unsaturated polyester (UP) has been increased to 289~334 DEG C from 255 DEG C, most fast decomposition rate
Temperature be also increased to 400~414 DEG C from 395 DEG C.
Table 2 is the tensile strength and elongation at break data of unsaturated polyester modified front and back.From table 2 it can be seen that modified
The tensile strength of unsaturated polyester (UP) afterwards is obviously improved, while elongation at break variation is little.
The Thermogravimetric Data of 1 embodiment 1-4 of table, 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 |
The tensile strength and elongation at break data of the unsaturated polyester modified front and back of table 2
Claims (5)
1. a kind of preparation method for the modified unsaturated polyester resin that heat resistance improves, which is characterized in that the modification is not
Saturated polyester resin is according to mass fraction meter, each material content are as follows: and 100 parts of unsaturated polyester resin, 5~25 parts of epoxy resin,
0.5~2.5 part of glycidyl methacrylate, 3~15 parts of epoxy curing agent, cyclohexanone peroxide-cobalt naphthenate 3~5
Part；
It is described the preparation method comprises the following steps:
(1) glycidyl methacrylate, epoxy resin and unsaturated polyester resin are weighed in flask, mechanical stirring 30min,
It weighs epoxy curing agent to be added in flask, with mechanical stirring 10min, is eventually adding cyclohexanone peroxide-cobalt naphthenate
Into flask, the mixture in flask is poured into beaker after stirring 1min, the above revolving speed is 500~600r/min；
(2) material in beaker is put into vacuum drying oven, bubble therein is removed by the method vacuumized；
(3) mixture by vacuumizing bubble removing is poured into Teflon mould, at normal temperature solidification 2 hours, so
Solidify under the conditions of 150 DEG C afterwards 6~10 hours and forms.
2. the preparation method for the modified unsaturated polyester resin that heat resistance as described in claim 1 improves, which is characterized in that
Epoxy resin described in step (1) is E51.
3. the preparation method for the modified unsaturated polyester resin that heat resistance as described in claim 1 improves, which is characterized in that
Epoxy curing agent described in step (1) is methyl tetrahydrophthalic anhydride.
4. the preparation method for the modified unsaturated polyester resin that heat resistance as described in claim 1 improves, which is characterized in that
Revolving speed described in step (1) is 550~580r/min.
5. the preparation method for the modified unsaturated polyester resin that heat resistance as described in claim 1 improves, which is characterized in that
Curing time is 8 hours under the conditions of 150 DEG C described in step (3).
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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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| CN106832155A CN106832155A (en) | 2017-06-13 |
| CN106832155B true CN106832155B (en) | 2018-12-07 |
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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 |
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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 |
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