CN109206561A - A method of unsaturated polyester resin is prepared with glycerol - Google Patents
A method of unsaturated polyester resin is prepared with glycerol Download PDFInfo
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- CN109206561A CN109206561A CN201811056158.5A CN201811056158A CN109206561A CN 109206561 A CN109206561 A CN 109206561A CN 201811056158 A CN201811056158 A CN 201811056158A CN 109206561 A CN109206561 A CN 109206561A
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- glycerol
- temperature
- polyester resin
- unsaturated polyester
- reaction kettle
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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
- 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
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention discloses a kind of method for preparing unsaturated polyester resin with glycerol, and by using glycerol substitution diol segment class as reactive matrix, heat resistance better unsaturated polyester resin can be synthesized while substituting glycols.For tool there are three hydroxyl, the heat resistance of the unsaturated polyester resin of synthesis is better than heat resistance, weatherability and the impact resistant strength of the unsaturated polyester resin of ethylene glycol production on the strand of glycerol；Its glycerol and benzoic acid are used as the end-capping group of linear molecule chain in the synthesis process, and the unsaturated linear polymer being synthesized is enabled to guarantee there is good compatibility with styrene；The from a wealth of sources of glycerol, price are low, and the triatomic alternative part of structure is worth synthesis material of the higher dihydric alcohol as unsaturated polyester resin, reduce production cost.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of to prepare unsaturated polyester resin with glycerol
Method.
Background technique
Unsaturated polyester resin is most common one kind in thermosetting resin, it is by monounsaturated dicarboxylic acid, unsaturated binary
Line polymer made of acid and dihydric alcohol polycondensation, diluted by cross-linking monomer or active solvent to be formed with certain viscosity
Resin solution has a good application prospect frequently as the substrate of coating, glass steel making and ornament manufacture.For producing
The raw material of unsaturated polyester resin mostly from petrochemical industry, belongs to non-renewable resource, with market demand greatly
Increase, the raw materials for production of unsaturated polyester resin need to find the substitute of resource abundance, ethylene glycol, propylene glycol, neopentyl glycol etc.
Glycols occupies very big specific gravity in its synthesis material, and often need to excessively add guarantee and sufficiently react with acid anhydrides, is produced into
This height, find it is a kind of can apply the glycols raw material substitute of synthesis unsaturated polyester resin be in this field one it is important
Research direction.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of method for preparing unsaturated polyester resin with glycerol, lead to
It crosses and uses glycerol substitution diol segment class as reactive matrix, it is more preferable to synthesize heat resistance while substituting glycols
Unsaturated polyester resin.
The technical scheme adopted by the invention to achieve the purpose is as follows:
A method of unsaturated polyester resin, including following implementation steps are prepared with glycerol:
S1. each ingredient is accurately weighed by component prescription, sequentially adds glycerol, benzoic acid, catalyst, nitrogen in a kettle
Pump installation is with 0.4~0.5m3The speed of/h pours nitrogen to reaction kettle, is in reaction system in nitrogen atmosphere, is condensed back
Device supplies water, and is slowly heated up with the speed of 15~20 DEG C/h, while starting agitating device and starting to stir, when condensation reflux unit
When evaporating temperature rise to 98~102 DEG C, holding evaporates temperature and maintains 98~102 DEG C, when temperature of reaction kettle is warming up to 200~210 DEG C, protects
Constant temperature sustained response is held, after 2~4 hours, temperature of reaction kettle is made to be down to 135~150 DEG C；
S2. each ingredient is accurately weighed by component prescription, sequentially adds maleic anhydride, phthalic acid in a kettle
Acid anhydride, diethylene glycol (DEG) continue to heat up with the speed of 10~15 DEG C/h, when condensation reflux unit water outlet, stop supply nitrogen, start to take out
Vacuum, when temperature of reaction kettle is up to 198~205 DEG C, keeping constant temperature, the reaction was continued；
S3. when the acid value of reaction system in reaction kettle is to 20~30mgKOH/g, viscosity up to 500~600cps, stop plus
Heat starts to cool down, and when being down to 165~180 DEG C to temperature of reaction kettle, stops vacuumizing, and polymerization inhibitor is added, paraffin is sufficiently stirred
Afterwards, temperature of reaction kettle is down to 150~155 DEG C of heat preservations；
S4. addition styrene, defoaming agent are stirred in dilution kettle, and mixture obtained by S3, stirring is added to dilution kettle
After uniformly dispersing each component, continues to cool down, be cooled to 35~50 DEG C, products therefrom is packaged.
Further illustrate, the step S1 into S4 each ingredient based on following mass percent: glycerol 5~7%, two
Glycol 10~13%, benzoic acid 6~8%, maleic anhydride 12~15%, phthalic anhydride 12~15%, catalyst
0.005~0.02%, polymerization inhibitor 0.04~0.06%, paraffin 0.005~0.02%, defoaming agent 0.01~0.02%, styrene
42~55%.
It further illustrates, the catalyst is one or both of dibutyl tin, stannous octoate.
It further illustrates, the polymerization inhibitor is one or both of hydroquinone, adjacent methyl hydroquinone.
Compared with prior art, the beneficial effects of the present invention are:
(1) there are three hydroxyls, the heat resistance of the unsaturated polyester resin of synthesis to be better than second for tool on the strand of glycerol
Heat resistance, weatherability and the impact resistant strength of the unsaturated polyester resin of glycol production；Its glycerol and benzoic acid are in synthesis process
The middle end-capping group as linear molecule chain enables the unsaturated linear polymer being synthesized to guarantee and benzene second
Alkene has good compatibility.
(2) the from a wealth of sources of glycerol, price are low, and the triatomic alternative part of structure is worth higher dihydric alcohol conduct
The synthesis material of unsaturated polyester resin, reduces production cost.
Specific embodiment
In order to further understand the content, features and effects of the present invention, hereby enumerating following embodiment explanation.
Embodiment 1
Experimental provision: use four mouthfuls of ground flasks of 500ml capacity as reaction kettle, supplied configured with temperature regulating device, nitrogen
To device, condensation reflux unit, vacuum evacuation device, agitating device, thermometer；Made using three mouthfuls of ground flasks of 500ml capacity
To dilute kettle, it is configured with temperature regulating device, thermometer, agitating device.
Experimentation:
S1. glycerol 15g, benzoic acid 18g, catalyst 0.045g are added in a kettle, accesses nitrogen ingress pipe, nitrogen pump
Device pours nitrogen to reaction kettle with the speed of 0.5m3/h, is in reaction system in nitrogen atmosphere, and condensation reflux unit supplies
Water is slowly heated up with the speed of 20 DEG C/h, while being started agitating device and being started to stir, and condensation reflux unit evaporates temperature rise to 100
DEG C when, holding evaporates temperature and maintains 100 DEG C, and temperature of reaction kettle heats up 205 DEG C, keeps constant temperature sustained response；
S2. after isothermal reaction 2.4 hours, so that temperature of reaction kettle is down to 145 DEG C, sequentially add maleic two in a kettle
Acid anhydrides 39g, phthalic anhydride 40g, diethylene glycol (DEG) 33g continue to heat up with the speed of 15 DEG C/h, when condensation reflux unit is discharged
When, stop supply nitrogen, open vacuum evacuation device, when temperature of reaction kettle is up to 205 DEG C, keeping constant temperature, the reaction was continued；
S3. when the acid value of reaction system in reaction kettle is to 29mgKOH/g, viscosity reaches 533cps, stops heating, starts to drop
Temperature, temperature of reaction kettle are down to 165 DEG C, stop vacuumizing, after addition polymerization inhibitor 0.15g, paraffin 0.045g are sufficiently stirred, reaction kettle
Temperature is down to 150 DEG C of heat preservations；
S4. styrene 138g, 0.04g defoaming agent is added in dilution kettle to be stirred, reaction kettle institute is added to dilution kettle
Mixture is obtained, is stirred evenly after dispersing each component, is continued to cool down, be cooled to 35 DEG C, obtain 1 resin sample of embodiment.
Embodiment 2
Experimental provision is the same as embodiment 1.
Experimentation:
S1. glycerol 17g, benzoic acid 20g, catalyst 0.054g are added in a kettle, accesses nitrogen ingress pipe, nitrogen pump
Device pours nitrogen to reaction kettle with the speed of 0.5m3/h, is in reaction system in nitrogen atmosphere, and condensation reflux unit supplies
Water is slowly heated up with the speed of 20 DEG C/h, while being started agitating device and being started to stir, and condensation reflux unit evaporates temperature rise to 100
DEG C when, holding evaporates temperature and maintains 100 DEG C, and temperature of reaction kettle heats up 205 DEG C, keeps constant temperature sustained response；
S2. after isothermal reaction 2.6 hours, so that temperature of reaction kettle is down to 145 DEG C, sequentially add maleic two in a kettle
Acid anhydrides 41g, phthalic anhydride 42.3g, diethylene glycol (DEG) 34.5g continue to heat up with the speed of 15 DEG C/h, when condensation reflux unit goes out
When water, stop supply nitrogen, open vacuum evacuation device, when temperature of reaction kettle is up to 205 DEG C, keeping constant temperature, the reaction was continued；
S3. when the acid value of reaction system in reaction kettle is to 26mgKOH/g, viscosity reaches 552cps, stops heating, starts to drop
Temperature, temperature of reaction kettle are down to 165 DEG C, stop vacuumizing, after addition polymerization inhibitor 0.15g, paraffin 0.045g are sufficiently stirred, reaction kettle
Temperature is down to 150 DEG C of heat preservations；
S4. styrene 151g, 0.04g defoaming agent is added in dilution kettle to be stirred, reaction kettle institute is added to dilution kettle
Mixture is obtained, is stirred evenly after dispersing each component, is continued to cool down, be cooled to 35 DEG C, obtain 2 resin sample of embodiment.
Embodiment 3
Experimental provision is the same as embodiment 1.
Experimentation:
S1. glycerol 18.6g, benzoic acid 21.9g, catalyst 0.06g are added in a kettle, accesses nitrogen ingress pipe, nitrogen
Air pump device pours nitrogen to reaction kettle with the speed of 0.5m3/h, is in reaction system in nitrogen atmosphere, condensation reflux unit
It supplies water, is slowly heated up with the speed of 20 DEG C/h, while starting agitating device and starting to stir, condensation reflux unit evaporates temperature rise extremely
At 100 DEG C, holding evaporates temperature and maintains 100 DEG C, and temperature of reaction kettle heats up 205 DEG C, keeps constant temperature sustained response；
S2. after isothermal reaction 2.6 hours, so that temperature of reaction kettle is down to 145 DEG C, sequentially add maleic two in a kettle
Acid anhydrides 42.1g, phthalic anhydride 41.5g, diethylene glycol (DEG) 37.8g continue to heat up, work as condensation reflux unit with the speed of 15 DEG C/h
When water outlet, stop supply nitrogen, open vacuum evacuation device, when temperature of reaction kettle is up to 205 DEG C, keeping constant temperature, the reaction was continued；
S3. when the acid value of reaction system in reaction kettle is to 25mgKOH/g, viscosity reaches 572cps, stops heating, starts to drop
Temperature, temperature of reaction kettle are down to 165 DEG C, stop vacuumizing, after addition polymerization inhibitor 0.15g, paraffin 0.045g are sufficiently stirred, reaction kettle
Temperature is down to 150 DEG C of heat preservations；
S4. styrene 162g, 0.04g defoaming agent is added in dilution kettle to be stirred, reaction kettle institute is added to dilution kettle
Mixture is obtained, is stirred evenly after dispersing each component, is continued to cool down, be cooled to 35 DEG C, obtain 3 resin sample of embodiment.
Embodiment 4
Experimental provision is the same as embodiment 1.
Experimentation:
S1. glycerol 20.4g, benzoic acid 23.2g, catalyst 0.053g are added in a kettle, accesses nitrogen ingress pipe, nitrogen
Air pump device pours nitrogen to reaction kettle with the speed of 0.5m3/h, is in reaction system in nitrogen atmosphere, condensation reflux unit
It supplies water, is slowly heated up with the speed of 20 DEG C/h, while starting agitating device and starting to stir, condensation reflux unit evaporates temperature rise extremely
At 100 DEG C, holding evaporates temperature and maintains 100 DEG C, and temperature of reaction kettle heats up 205 DEG C, keeps constant temperature sustained response；
S2. after isothermal reaction 2.6 hours, so that temperature of reaction kettle is down to 145 DEG C, sequentially add maleic two in a kettle
Acid anhydrides 44.3g, phthalic anhydride 44.5g, diethylene glycol (DEG) 39g continue to heat up with the speed of 15 DEG C/h, when condensation reflux unit goes out
When water, stop supply nitrogen, open vacuum evacuation device, when temperature of reaction kettle is up to 205 DEG C, keeping constant temperature, the reaction was continued；
S3. when the acid value of reaction system in reaction kettle is to 23mgKOH/g, viscosity reaches 582cps, stops heating, starts to drop
Temperature, temperature of reaction kettle are down to 165 DEG C, stop vacuumizing, after addition polymerization inhibitor 0.15g, paraffin 0.045g are sufficiently stirred, reaction kettle
Temperature is down to 150 DEG C of heat preservations；
S4. styrene 162g, 0.04g defoaming agent is added in dilution kettle to be stirred, reaction kettle institute is added to dilution kettle
Mixture is obtained, is stirred evenly after dispersing each component, is continued to cool down, be cooled to 35 DEG C, obtain 4 resin sample of embodiment.
To above-described embodiment 1, into embodiment 4, resin sample carries out traditional performance detection and uses the resin sample system
Make casting matrix testing piece, measures the tensile property of casting matrix testing piece.
The traditional performance of resin sample is as shown in the table in embodiment 1 to embodiment 4:
| Finished product test name is thin | Unit | Numerical value | Measurement standard |
| Acid value (Acid value) | mgKOH/g | 20-28 | GB/T 2895-2008 |
| Viscosity (Viscosity) | cps | 250-550 | GB/T 7193-2008 |
| Gel time (Gel time) | min | 16-22 | GB/T 7193-2008 |
| Curing time (Minimum cure Time) | min | ≦35 | GB/T 7193-2008 |
| Exothermic peak (Top Temperature) | ℃ | 180-200 | GB/T 7193-2008 |
| Solid content (Solid content) | % | 63-70 | GB/T 7193-2008 |
| H2O% (Water sontent) | WT% | ≦0.13 | GB/T 7193-2008 |
By upper Biao Ke get, resin sample produced by the present invention has viscosity lower, and the gel solidification time is short, and solid content is high
Feature is readily able to processing and forming；Exothermic peak reaches 180-200 DEG C, heat-resisting after curing molding, weatherability is good.
The tensile property that casting matrix testing piece is made in embodiment 1 to embodiment 4 resin sample is as shown in the table:
| Test specimen number | Specimen width | Specimen thickness | Failing load | Tensile strength | Elongation at break | Elasticity modulus |
| mm | mm | N | Mpa | % | Mpa | |
| Embodiment 1 | 9.64 | 4.83 | 3211 | 68.96 | 3.9 | 3479.5 |
| Embodiment 2 | 9.64 | 4.75 | 2992 | 65.34 | 3.3 | 3445 |
| Embodiment 3 | 9.64 | 4.88 | 3226 | 68.58 | 4.1 | 3428 |
| Embodiment 4 | 9.64 | 4.95 | 3290 | 68.94 | 4.2 | 3316.5 |
As seen from the above table, there is preferable impact resistance using the casting matrix testing piece of the preparation of resin obtained by the present invention.
The above is only the preferred embodiments of the present invention, and is not intended to limit the present invention in any form,
Any simple modification made to the above embodiment according to the technical essence of the invention, equivalent variations and modification, belong to
The range of technical solution of the present invention.
Claims (4)
1. a kind of method for preparing unsaturated polyester resin with glycerol, which is characterized in that including following implementation steps:
S1. each ingredient is accurately weighed by component prescription, sequentially adds glycerol, benzoic acid, catalyst, nitrogen pump dress in a kettle
It sets with 0.4~0.5m3The speed of/h pours nitrogen to reaction kettle, is in reaction system in nitrogen atmosphere, condensation reflux unit
It supplies water, is slowly heated up with the speed of 15~20 DEG C/h, when condensation reflux unit is when evaporating temperature rise to 98~102 DEG C, and keep evaporating
Temperature maintains 98~102 DEG C, when temperature of reaction kettle is warming up to 200~210 DEG C, after constant temperature sustained response 2~4 hours, and reaction
Kettle temperature degree is down to 135~150 DEG C；
S2. each ingredient is accurately weighed by component prescription, sequentially adds maleic anhydride in a kettle, phthalic anhydride,
Diethylene glycol (DEG), starting agitating device start to stir, continue to heat up with the speed of 10~15 DEG C/h, when condensation reflux unit water outlet,
Stop supply nitrogen, when temperature of reaction kettle is up to 198~205 DEG C, the reaction was continued for constant temperature；
S3. when the acid value of reaction system in reaction kettle is to 20~30mgKOH/g, viscosity stops heating up to 500~600cps,
Start to cool down, when being down to 165~180 DEG C to temperature of reaction kettle, addition polymerization inhibitor, paraffin are sufficiently stirred, and temperature of reaction kettle is down to
150~155 DEG C, stop cooling；
S4. styrene is added in dilution kettle, mixture, defoaming agent obtained by S3 is added to dilution kettle, stirring evenly makes each component
After dispersion, continue to cool down, is cooled to 35~50 DEG C, products therefrom is packaged.
2. a kind of method for preparing unsaturated polyester resin with glycerol according to claim 1, it is characterised in that: described
Step S1 into S4 each ingredient based on following mass percent: glycerol 5~7%, diethylene glycol (DEG) 10~13%, benzoic acid 6~8%,
Maleic anhydride 12~15%, phthalic anhydride 12~15%, catalyst 0.005~0.02%, polymerization inhibitor 0.04~
0.06%, paraffin 0.005~0.02%, defoaming agent 0.01~0.02%, styrene 42~55%.
3. a kind of method for preparing unsaturated polyester resin with glycerol according to claim 1, it is characterised in that: described
Catalyst is one or both of dibutyl tin, stannous octoate.
4. a kind of method for preparing unsaturated polyester resin with glycerol according to claim 1, it is characterised in that: described
Polymerization inhibitor is one or both of hydroquinone, adjacent methyl hydroquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811056158.5A CN109206561A (en) | 2018-09-11 | 2018-09-11 | A method of unsaturated polyester resin is prepared with glycerol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811056158.5A CN109206561A (en) | 2018-09-11 | 2018-09-11 | A method of unsaturated polyester resin is prepared with glycerol |
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| CN109206561A true CN109206561A (en) | 2019-01-15 |
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| CN201811056158.5A Pending CN109206561A (en) | 2018-09-11 | 2018-09-11 | A method of unsaturated polyester resin is prepared with glycerol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092874A (en) * | 2019-04-23 | 2019-08-06 | 广西华砻树脂有限公司 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof for daylighting tile |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219882A (en) * | 2011-05-04 | 2011-10-19 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing glycerol |
| 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 |
| CN106832141A (en) * | 2017-02-24 | 2017-06-13 | 江苏赛鑫树脂有限公司 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
-
2018
- 2018-09-11 CN CN201811056158.5A patent/CN109206561A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219882A (en) * | 2011-05-04 | 2011-10-19 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing glycerol |
| 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 |
| CN106832141A (en) * | 2017-02-24 | 2017-06-13 | 江苏赛鑫树脂有限公司 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092874A (en) * | 2019-04-23 | 2019-08-06 | 广西华砻树脂有限公司 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof for daylighting tile |
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