CN106832141A - A kind of glycerin modification unsaturated polyester resin and preparation method thereof - Google Patents
A kind of glycerin modification unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN106832141A CN106832141A CN201710103067.1A CN201710103067A CN106832141A CN 106832141 A CN106832141 A CN 106832141A CN 201710103067 A CN201710103067 A CN 201710103067A CN 106832141 A CN106832141 A CN 106832141A
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- polyester resin
- unsaturated polyester
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- glycerine
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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
- 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
-
- 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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- 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 invention discloses a kind of glycerin modification unsaturated polyester resin for being applied to produce fiberglass mechanism daylighting tile and preparation method thereof, the dihydroxylic alcohols used in raw material of the present invention uses diethylene glycol (DEG) and determines that its parts by weight is 15 22 parts by test of many times, compared with prior art, unsaturated-resin reactivity of the present invention is high, easy completion of cure, low cost, resin cured matter good toughness, heat release are slow, heat endurance is good, synthesis technique is simple, it is with short production cycle, excellent product performance, environmental protection is produced without " three wastes ".
Description
Technical field
The present invention relates to a kind of unsaturated polyester resin, more particularly to it is applied to produce one kind of fiberglass mechanism daylighting tile
Glycerin modification unsaturated polyester resin and preparation method thereof.
Background technology
Unsaturated polyester resin typically has the line with ester bond and unsaturated double-bond of dihydroxylic alcohols and binary acid polycondensation
Property high molecular polymer, then different types of unsaturated polyester resin is formed after styrene monomer latting drown, unsaturated polyester (UP) tree
Fat possesses good workability, can solidify at room temperature, is molded under normal pressure, and processing performance flexibly, is particularly suitable for large-scale and existing
Field makes glass fiber reinforced plastics product, and product possesses good combination property after solidification, and price is excellent compared to other kinds of naval stores
Gesture is obvious.It is widely used, in the row such as vehicular traffic, building, shipbuilding, chemical industry equipment, electronic apparatus, sports equipment and articles for daily use
Industry has application, is occupied an important position in composite industry.
A kind of high-performance composite materials that FRP daylighting tiles are made up of unsaturated polyester resin and glass fibre, it is extensive
It is applied to the fields such as the daylighting of industrial premises roofing metope, the daylighting of agriculture vegetable booth thermal insulation, Public Physical Education venue roofing daylighting.Mesh
The preceding country is very big with unsaturated polyester resin demand to daylighting tile, it is contemplated that with the reduction of oil reserve, petrochemical industry
The price of product sharp rises, and the production cost of unsaturated polyester resin is also growing day by day, and petrochemicals are multipair greatly in addition
Environment has very big pollution, on the premise of environmental protection, finds cheap, and the feedstock alternative of environmental protection just turns into one
Individual important topic.
A kind of glycerin modification unsaturated polyester (UP) tree is disclosed in Chinese patent application prospectus, in CN103289068A
The preparation method of fat.The preparation method includes polycondensation reaction and cross-linking reaction, it is characterised in that organotin is added in polycondensation reaction
Class catalyst.（1）Polycondensation reaction：Under high pure nitrogen protection, by glycerine, dihydroxylic alcohols, monounsaturated dicarboxylic acid, saturation monoacid, anti-
Oxygen agent and organic tin catalyst input stir with thermometer, agitator, the reactor of condenser, are warming up to thing
Material water outlet, 0.5-1.5 hours is incubated at 160-180 DEG C；After insulation terminates, 200-210 DEG C is warming up to until acid number drops to
Below 20mgKOH/g, is then cooled to 155-165 DEG C of input unsaturated dibasic acid, material water outlet is warming up to, at 160-180 DEG C
Insulation 0.5-1.5 hours；After insulation terminates, 200-210 DEG C is warming up to up to acid number drops to below 58mgKOH/g, in vacuum
Polycondensation to acid number is less than 40mgKOH/g under degree -0.07--0.098MPa, is cooled to 180 DEG C of addition polymerization inhibitors；（2）Cross-linking reaction：
120-130 DEG C of addition crosslinkable monomers are cooled to, product glycerin modification unsaturated polyester resin is obtained final product after stirring.
But the preparation method preparation process temperature is repeatedly lifted repeatedly, and to temperature controlled processes higher, the technique of requirement
Complexity is higher to personnel's practical operation requirement.
The content of the invention
The technical problem to be solved in the present invention is to provide that a kind of course of reaction is relatively easy and cheap, environmental protection
Daylighting tile unsaturated polyester resin and preparation method thereof.
To solve the above problems, the invention provides a kind of glycerin modification unsaturated polyester resin, raw materials by weight portion
It is calculated as：
Diethylene glycol (DEG) 15-22 parts
Glycerine 10-15 parts
Benzoic acid 4-8 parts
Phthalic anhydride 10-15 parts
Maleic anhydride 15-20 parts
Styrene 38-42 parts
Hydroquinones 0.02-0.05 parts
The preparation method of glycerin modification unsaturated polyester resin of the present invention, it is comprised the following steps that：
（1）Polycondensation reaction：Put into diethylene glycol (DEG), benzoic acid, phthalic anhydride, maleic anhydride, benzene second successively by formula ratio
Alkene, glycerine, logical nitrogen heat to 170 DEG C and start stirring, after insulation 1h, are continuously heating to 215 DEG C, and control heats up fast
Degree, keeps 14-16 DEG C/h of programming rate, controls vertical 100-103 DEG C of column temperature, and material temperature is incubated 2h after being raised to 215 DEG C,
Detection acid number, viscosity vacuumize dehydration after reaching requirement, until acid number viscosity reaches the endpoint of regulation.
（2）Cross-linking reaction：130 DEG C are cooled to, auxiliary addition agent hydroquinones is thrown, latting drown obtains final product product sweet after stirring
Oily modified unsaturated polyester resin.
As a further improvement on the present invention, the inoxidizability of daylighting tile is made to improve, is added during cross-linking reaction
Plus peroxide agent, parts by weight are calculated as：0.002-0.005 parts, the peroxide agent is peroxidating ring the sixth of the twelve Earthly Branches ketone, isopropylbenzene peroxidating
One or more in hydrogen, dichloro peroxidating first milling.
The dihydroxylic alcohols used in raw material of the present invention uses diethylene glycol (DEG) and determines that its parts by weight is 15-22 parts by test of many times,
Unsaturated-resin reactivity is high, easy completion of cure, low cost, and resin cured matter good toughness, heat release are slow, heat endurance is good.
Resin reaction time and other performance comparisons such as following table using the proportioning：
The beneficial effects of the invention are as follows：Compared with prior art, synthesis technique of the present invention is simple, with short production cycle, properties of product
Excellent, environmental protection is produced without " three wastes ".
Specific embodiment
The present invention is described further with reference to embodiments.
Comparative example one：Composition of raw materials is as follows：（1）12 parts of glycerine,（2）16 parts of ethylene glycol,（3）9 parts of propane diols,（4）Benzene first
8 parts of acid,（5）15 parts of M-phthalic acid,（6）0.006 part of antioxidant,（7）0.0078 part of dibutyl tin,（8）Maleic acid 15
Part,（9）0.0096 part of hydroquinones,（10）40 parts of styrene.Under high pure nitrogen protection, will by above-mentioned formula（1）~（7）
Input stirs with thermometer, agitator, the reactor of condenser.It is rapidly heated to material water outlet, in 160 DEG C of guarantors
Temperature 0.5 hour.Insulation is slow after terminating to heat up, and is warming up to 200 DEG C of polycondensation reactions until acid number drops to below 20mgKOH/g.
Then 155 DEG C of inputs are cooled to（8）, it is brought rapidly up to material water outlet, it is incubated 0.5 hour at 160 DEG C.Insulation is slow after terminating to rise
Temperature, is warming up to 200 DEG C of polycondensation reactions until acid number drops to below 58mgKOH/g, and polycondensation is to acid under vacuum -0.07MPa
Value is less than 40mgKOH/g, is cooled to 180 DEG C of additions（9）, it is cooled to 120 DEG C of additions（10）, product glycerine is obtained final product after stirring
Modified unsaturated polyester resin.
Comparative example two：With four mouthfuls of ground flasks of 1000ml as reactor, thermometer, electric stirring have been respectively mounted
Device, nitrogen ingress pipe and fractionating device, put into glycerine 80g, diethylene glycol (DEG) 150g, benzoic acid 40g, phthalic anhydride successively
100g, maleic anhydride 190g, hydroquinones 0.2g.Then gradually heated up in the case where nitrogen is passed through, evaporate a temperature control
System is below 100-103 DEG C.Start insulation reaction when kettle temperature reaches 215 DEG C, acid number is controlled in below 50-55mgKOH/g
Start to vacuumize, until acid number 22-25mgKOH/g.Material is down to less than 170 DEG C and adds hydroquinones 0.2g.It is cooled to again
Less than 130 DEG C addition styrene 380g, stir, and latting drown temperature control is between 70-80 DEG C.Testing index is qualified
After be cooled to 50-60 DEG C of filtering and obtain final product faint yellow muddy viscous liquid.
Comparative example three：Other raw material numbers are constant, diethylene glycol (DEG) 300g, prepared by the process of comparative example two, obtain glycerin modification
Unsaturated polyester resin.
Embodiment one:Other raw material numbers are constant, diethylene glycol (DEG) 120g, prepared by the process of comparative example two, obtain glycerin modification
Unsaturated polyester resin.
Embodiment two：Other raw material numbers are constant, diethylene glycol (DEG) 220g, prepared by the process of comparative example two, obtain glycerin modification
Unsaturated polyester resin.
Comparative example and the reaction time and other performance comparisons such as following table of implementing profit：
To sum up, other parts by weight of raw material are constant, when diethylene glycol (DEG) parts by weight are between 15-22, the comprehensive polycondensation time it is shorter and
Acid number is minimum.
Claims (3)
1. a kind of glycerin modification unsaturated polyester resin, it is characterised in that described raw materials by weight portion is calculated as：
Diethylene glycol (DEG) 15-22 parts
Glycerine 10-15 parts
Benzoic acid 4-8 parts
Phthalic anhydride 10-15 parts
Maleic anhydride 15-20 parts
Styrene 38-42 parts
Hydroquinones 0.02-0.05 parts.
2. polyester resin according to claim 1, it is characterised in that：Peroxide agent, weight are added during cross-linking reaction
Amount number is calculated as 0.002-0.005 parts, and the peroxide agent is peroxidating ring the sixth of the twelve Earthly Branches ketone, isopropyl benzene hydroperoxide, dichloro peroxidating
One or more in first milling.
3. a kind of preparation method of glycerin modification unsaturated polyester resin, it is characterised in that：The preparation method includes polycondensation reaction
And cross-linking reaction, comprise the following steps that：
（1）Polycondensation reaction：Polyester formulation's amount as described in claim 1 puts into diethylene glycol (DEG), benzoic acid, O-phthalic successively
Acid anhydrides, maleic anhydride, styrene, glycerine, logical nitrogen heat to 170 DEG C and start stirring, after insulation 1h, continue to rise
Temperature controls programming rate to 215 DEG C, keeps 7-8 DEG C/h of programming rate, controls vertical 100-103 DEG C of column temperature, material temperature
2h is incubated after being raised to 215 DEG C, detection acid number, viscosity vacuumize dehydration after reaching requirement, until acid number viscosity reaches the end of regulation
Point index；
（2）Cross-linking reaction：130 DEG C are cooled to, auxiliary addition agent hydroquinones is thrown, latting drown obtains final product product glycerine and changes after stirring
Property unsaturated polyester resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710103067.1A CN106832141A (en) | 2017-02-24 | 2017-02-24 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710103067.1A CN106832141A (en) | 2017-02-24 | 2017-02-24 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
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| CN106832141A true CN106832141A (en) | 2017-06-13 |
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| CN201710103067.1A Pending CN106832141A (en) | 2017-02-24 | 2017-02-24 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206561A (en) * | 2018-09-11 | 2019-01-15 | 惠州市固德尔合成材料有限公司 | A method of unsaturated polyester resin is prepared with glycerol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307930A (en) * | 2000-04-27 | 2001-11-02 | Toshiba Chem Corp | Coil impregnating resin composition |
| CN103289068A (en) * | 2013-05-21 | 2013-09-11 | 山东宏信化工股份有限公司 | Preparation method of glycerinum modified unsaturated polyester resin |
| CN103951793A (en) * | 2014-04-15 | 2014-07-30 | 吴桥昊通树脂有限公司 | Method for producing unsaturated polyester resin by using glycerinum |
-
2017
- 2017-02-24 CN CN201710103067.1A patent/CN106832141A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307930A (en) * | 2000-04-27 | 2001-11-02 | Toshiba Chem Corp | Coil impregnating resin composition |
| CN103289068A (en) * | 2013-05-21 | 2013-09-11 | 山东宏信化工股份有限公司 | Preparation method of glycerinum modified unsaturated polyester resin |
| CN103951793A (en) * | 2014-04-15 | 2014-07-30 | 吴桥昊通树脂有限公司 | Method for producing unsaturated polyester resin by using glycerinum |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206561A (en) * | 2018-09-11 | 2019-01-15 | 惠州市固德尔合成材料有限公司 | A method of unsaturated polyester resin is prepared with glycerol |
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Application publication date: 20170613 |