CN102443114A - Air-dried unsaturated polyester resin with excellent comprehensive property and its preparation method - Google Patents
Air-dried unsaturated polyester resin with excellent comprehensive property and its preparation method Download PDFInfo
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- CN102443114A CN102443114A CN2010105057188A CN201010505718A CN102443114A CN 102443114 A CN102443114 A CN 102443114A CN 2010105057188 A CN2010105057188 A CN 2010105057188A CN 201010505718 A CN201010505718 A CN 201010505718A CN 102443114 A CN102443114 A CN 102443114A
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Abstract
The invention relates to a high-molecular material preparation technical field, especially relates to an air-dried unsaturated polyester resin with excellent comprehensive property and its preparation method. The air-dried unsaturated polyester resin with excellent comprehensive property is prepared by the processes that organic polyalcohol, reproducible vegetable fat, DCPD and an addition product of maleic anhydride, micromolecule dihydric alcohol diacid and epoxy resin are subjected to ester exchange, polycondensation, and ring-opening reaction to form a polymer, and then the polymer is dissolved in styrene. The invention has the advantages that 1) the reproducible vegetable fat is taken as a main component, the usage of toxic chemical raw material can be reduced, therefore the idea for environmental protection is conformed. 2) the price of the raw materials is low, so that the preparation cost is low; 3) plant oil and DCPD in resin component provide good air-drying property, resin can be widely used in the field which possesses high requirement on air-drying property; 4) epoxy resin is used for modifying synthetic resin, so that adhesive ability, aging resistance, water resistance and chemical corrosion resistance of the product can be enhanced. The polyester resin of the invention can be used in the fields of paint, putty and composite materials.
Description
Technical field
The present invention relates to field of polymer material preparing technology, air-dried unsaturated polyester resin of especially a kind of excellent combination property and preparation method thereof.
Background technology
Unsaturated polyester resin is the most frequently used a kind of in the thermosetting resin, and it is the line polymer that is formed by monounsaturated dicarboxylic acid, unsaturated dibasic acid and divalent alcohol polycondensation, the resin solution with certain viscosity that forms through cross-linking monomer or strong solvent dilution.It is one of kind of consumption maximum in thermosetting resin and the glass fiber reinforced plastics composite material goods, because its production technique is easy, and the mechanics of product, electricity, the corrosion-resistant excellent performance that waits is widely used.But resin number of applications industrial chemicals; Improve use cost and waste the resource pollution environment; Therefore renewable resources fully is applied to the important trend that the resin field is development; Can influence practical application effect because airborne oxygen exists and causes that curing not exclusively is clamminess etc. in the general in addition curable unsaturated polyester process, also have much room for improvement.
In recent years,, there is a lot of methods to be used,, is widely used in the prescription of coating resin as adding the air-drying property that the allyl ether series monomer can improve product preferably in order to improve air-drying property, but monomer expensive comparatively speaking, and cost is than higher; Add a spot of paraffin, utilize wax in resin, slowly to rise to the surface, so secluding air, improve state of cure and empty dryness, but the wax that floats on the surface can reduce interlayer adhesion, cause the multi-layer product bonding force not enough; Also have some to use plastics film to cover resin surface and come secluding air, but increased the operation and the cost of technology; The report that used this low-cost product of DCPD to improve the product air-drying property in recent years gets more and more; Study on Correlative Mechanisms also has more report; It is mainly derived from the by product C 5 fraction and coal tar of petroleum cracking system ethylene industry, utilizes DCPD for the unsaturated polyester resin of material modification significantly raising being arranged all aspect thermotolerance, water tolerance, chemical resistance and the air-drying property.
Utilize at present DCPD mainly to concentrate on the affixture and the copolymerization of small molecules diacid glycol with itself and cis-butenedioic anhydride in the patent of report and the document;, performance passes through to use m-phthalic acid after reaching the upper limit; The monomer that prices such as NSC 6366 are more expensive further improves the resin rerum natura; Synthetic thinking is relatively limited to, and cost is also higher relatively, therefore seek a kind of excellent combination property and lower-cost compound method and be have theoretical and market ambiguous.
Summary of the invention
Relatively limit in order to overcome the synthetic thinking of existing unsaturated polyester resin, the deficiency that cost is also higher relatively the invention provides air-dried unsaturated polyester resin of a kind of excellent combination property and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is: a kind of air-dried unsaturated polyester resin of excellent combination property; It is through transesterify by the affixture of organic polyhydric alcohol, renewable Vegetable oil lipoprotein, DCPD and cis-butenedioic anhydride and small molecules divalent alcohol diprotic acid, epoxy resin; Polycondensation, the polymkeric substance that forms after the ring-opening reaction are dissolved in vinylbenzene and make.
According to another embodiment of the invention; Comprise that further said organic polyhydric alcohol content is 5.0 ~ 6.0mol; Renewable Vegetable oil lipoprotein content is 2.5 ~ 7.2mol; The affixture consumption of DCPD and cis-butenedioic anhydride is 15.0 ~ 65.0mol, each 1.0 ~ 5.0mol of small molecules diprotic acid divalent alcohol, epoxy resin 1.0 ~ 10.0mol.
According to another embodiment of the invention, comprise that further said organic polyhydric alcohol comprises one or more of TriMethylolPropane(TMP), USP Kosher or tetramethylolmethane; Said renewable Vegetable oil lipoprotein comprises tung oil, oleum lini, Oleum Cocois, Semen Maydis oil, Viscotrol C, peanut oil, sunflower seed oil, rapeseed oil, plam oil, soya-bean oil, oil extracted from rice husks etc., one or more in preferred tung oil, oleum lini and the soya-bean oil; Said small molecules divalent alcohol diprotic acid is meant and comprises Ucar 35, glycol ether, terepthaloyl moietie, methyl propanediol, NSC 6366, phthalic anhydride, cis-butenedioic anhydride, hexanodioic acid etc.
A kind of preparation method of air-dried unsaturated polyester resin of excellent combination property is characterized in that, it may further comprise the steps:
A, transesterification reaction:
The pure and mild renewable Vegetable oil lipoprotein of organic multicomponent is carried out transesterification reaction under certain reaction conditions, catalyzer has one or more in Lithium Hydroxide MonoHydrate, calcium hydroxide, Pottasium Hydroxide, sodium hydroxide, yellow soda ash, sodium hydrogencarbonate or the plumbous oxide;
The preparation of the affixture of B, DCPD and cis-butenedioic anhydride:
In temperature is under 80 ~ 125 ℃, and water and cis-butenedioic anhydride hydrolysis in reactor drum are generated along acid, DCPD is dripped in the into suitable acid again, keeps temperature of reaction between 120 ~ 140 ℃; Or DCPD and cis-butenedioic anhydride mixed in reactor drum, drip water again and generate said affixture;
C, polycondensation:
In the affixture and part small molecules divalent alcohol or the container of diprotic acid with DCPD and cis-butenedioic anhydride by certain reaction conditions adding vegetables oil ester exchange offspring; And have device and whipping appts, and feed nitrogen protection, stir and be warming up to water outlet; 95 ~ 105 ℃ of temperature and 170 ~ 210 ℃ of temperature of reaction are heated up in a steamer in control; To target viscosities, promptly bubble is managed viscosity O ~ Q, 150 ℃ of about 10 ± 2 pools of cone-plate;
D, ring-opening reaction:
Epoxy resin and polycondensation product are carried out ring-opening reaction under certain temperature and catalyst action, control stable reaction conditions to target acid number 15 ~ 30mgKOH/g.
E, finished product:
The polymkeric substance that above-mentioned reaction is obtained is dissolved in the air-dried unsaturated polyester resin that vinylbenzene makes excellent combination property.
According to another embodiment of the invention; Comprise that further the certain reaction conditions in the said steps A refers to that the molar ratio of the pure and mild renewable Vegetable oil lipoprotein of organic multicomponent is 1:0.5 ~ 1:1.2; 180 ~ 240 ℃ of temperature of reaction, nitrogen protection, the preferred Lithium Hydroxide MonoHydrate of catalyzer; Reaction detects patience with product and methyl alcohol volume ratio 1/3, and clarifying no phase-splitting is terminal point.
According to another embodiment of the invention; Comprise that further the certain reaction conditions among the said step C refers to that DCPD and cis-butenedioic anhydride affixture and ester exchange offspring are 1:0.2 ~ 1:0.5 in molar ratio, heat up in a steamer 95 ~ 105 ℃ of temperature, 170 ~ 210 ℃ of temperature of reaction; Use resin/vinylbenzene=2/1 preparation sample; With bubble pipe viscosity or cone-and-plate viscometer controlled target value, reaction end is O ~ Q, 150 ℃ of about 10 ± 2 pools of cone-plate.
According to another embodiment of the invention, comprise that further the epoxy resin among the said step D is one or more mixtures of E55, E51, E44, E42, E35.
According to another embodiment of the invention, comprise that further the certain temperature among the said step D refers to that temperature of reaction is 90 ~ 130 ℃.
According to another embodiment of the invention; Further comprise catalyzer among the said step D be quaternary ammonium salt, tertiary ammonium salt, alkali, salt, like benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, N, accelerine, benzyldimethylamine, benzyl diethylamine, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetramethyl ammonium chloride, 4 bromide, tetraphenylphosphonibromide bromide and catalyzer benzyltriethylammoinium chloride.
The invention has the beneficial effects as follows that air-drying property of the present invention is good, performances such as ageing-resistant, water-fast, corrosion-resistant and sticking power are all very excellent.Resin of the present invention can be applied in field and field of compound material that coating, putty etc. are had relatively high expectations to air-drying property, and toughness, sticking power, weathering resistance etc. are all very outstanding.Advantage of the present invention is: (1) is selected renewable Vegetable oil lipoprotein for use is the main body component, reduces the use of toxic industrial chemicals, meets the theory of environmental protection; (2) be made up of the lower raw material of price, preparation cost is cheap; (3) vegetables oil in the resin Composition and DCPD etc. provide good air-drying property, resin can be widely used in the field that empty dryness is had relatively high expectations; (4) use epoxy resin to the further modification of synthetic resins, improve sticking power, stability to aging, the water-fast and resistance to chemical attack of product.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Like Fig. 1 is synthesis technique synoptic diagram of the present invention.
Embodiment
Like Fig. 1 is synthesis technique synoptic diagram of the present invention; A kind of air-dried unsaturated polyester resin of excellent combination property; It is through transesterify by the affixture of organic polyhydric alcohol, renewable Vegetable oil lipoprotein, DCPD and cis-butenedioic anhydride and small molecules divalent alcohol diprotic acid, epoxy resin; Polycondensation, the polymkeric substance that forms after the ring-opening reaction are dissolved in vinylbenzene and make.
Said organic polyhydric alcohol content is 5.0 ~ 6.0mol, and renewable Vegetable oil lipoprotein content is 2.5 ~ 7.2mol, and the affixture consumption of DCPD and cis-butenedioic anhydride is 15.0 ~ 65.0mol, each 1.0 ~ 5.0mol of small molecules diprotic acid divalent alcohol, epoxy resin 1.0 ~ 10.0mol.
Said organic polyhydric alcohol comprises one or more of TriMethylolPropane(TMP), USP Kosher or tetramethylolmethane; Said renewable Vegetable oil lipoprotein comprises tung oil, oleum lini, Oleum Cocois, Semen Maydis oil, Viscotrol C, peanut oil, sunflower seed oil, rapeseed oil, plam oil, soya-bean oil, oil extracted from rice husks etc., one or more in preferred tung oil, oleum lini and the soya-bean oil; Said small molecules divalent alcohol diprotic acid is meant and comprises Ucar 35, glycol ether, terepthaloyl moietie, methyl propanediol, NSC 6366, phthalic anhydride, cis-butenedioic anhydride, hexanodioic acid etc.
A kind of preparation method of air-dried unsaturated polyester resin of excellent combination property, it may further comprise the steps:
A, transesterification reaction:
The pure and mild renewable Vegetable oil lipoprotein of organic multicomponent is carried out transesterification reaction under certain reaction conditions, catalyzer has one or more in Lithium Hydroxide MonoHydrate, calcium hydroxide, Pottasium Hydroxide, sodium hydroxide, yellow soda ash, sodium hydrogencarbonate or the plumbous oxide;
The preparation of the affixture of B, DCPD and cis-butenedioic anhydride:
In temperature is under 80 ~ 125 ℃, and water and cis-butenedioic anhydride hydrolysis in reactor drum are generated along acid, DCPD is dripped in the into suitable acid again, keeps temperature of reaction between 120 ~ 140 ℃; Or DCPD and cis-butenedioic anhydride mixed in reactor drum, drip water again and generate said affixture;
C, polycondensation:
In the affixture and part small molecules divalent alcohol or the container of diprotic acid with DCPD and cis-butenedioic anhydride by certain reaction conditions adding vegetables oil ester exchange offspring; And have device and whipping appts, and feed nitrogen protection, stir and be warming up to water outlet; 95 ~ 105 ℃ of temperature and 170 ~ 210 ℃ of temperature of reaction are heated up in a steamer in control; To target viscosities, promptly bubble is managed viscosity O ~ Q, 150 ℃ of about 10 ± 2 pools of cone-plate;
D, ring-opening reaction:
Epoxy resin and polycondensation product are carried out ring-opening reaction under certain temperature and catalyst action, control stable reaction conditions to target acid number 15 ~ 30mgKOH/g.
E, finished product:
The polymkeric substance that above-mentioned reaction is obtained is dissolved in the air-dried unsaturated polyester resin that vinylbenzene makes excellent combination property.
Certain reaction conditions in the said steps A refers to that the molar ratio of the pure and mild renewable Vegetable oil lipoprotein of organic multicomponent is 1:0.5 ~ 1:1.2; 180 ~ 240 ℃ of temperature of reaction; Nitrogen protection; The preferred Lithium Hydroxide MonoHydrate of catalyzer, reaction detects patience with product and methyl alcohol volume ratio 1/3, and clarifying no phase-splitting is terminal point.
Certain reaction conditions among the said step C refers to that DCPD and cis-butenedioic anhydride affixture and ester exchange offspring are 1:0.2 ~ 1:0.5 in molar ratio; Heat up in a steamer 95 ~ 105 ℃ of temperature; 170 ~ 210 ℃ of temperature of reaction are used resin/vinylbenzene=2/1 preparation sample, with bubble pipe viscosity or cone-and-plate viscometer controlled target value; Reaction end is O ~ Q, 150 ℃ of about 10 ± 2 pools of cone-plate.
Epoxy resin among the said step D is one or more mixtures of E55, E51, E44, E42, E35.
Certain temperature among the said step D refers to that temperature of reaction is 90 ~ 130 ℃.
Catalyzer among the said step D is quaternary ammonium salt, tertiary ammonium salt, alkali, salt, like benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, N, accelerine, benzyldimethylamine, benzyl diethylamine, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetramethyl ammonium chloride, 4 bromide, tetraphenylphosphonibromide bromide and catalyzer benzyltriethylammoinium chloride.
Said DCPD is a NSC 7352.
The inventor is through extensive and deep research; Through improving synthesis technique and prescription, obtain to have the air-drying property unsaturated polyester and the working method thereof of excellent combination property, product gel time and exothermic peak are all more suitable; Air-drying property is better; Shrinking percentage is low, and storage stability is good, and actual operation is stronger.
Below in conjunction with specific examples the present invention is done further explain, but the invention is not restricted to specific embodiment.
The synthetic embodiment of unsaturated polyester resin:
Prepare a kind of air-dried unsaturated polyester resin by following composition of raw materials and preparation method with excellent combination property.
Prescription is:
| Title | Quality |
| Tetramethylolmethane | 761 g |
| Oleum lini | 3060 g |
| Cis-butenedioic anhydride | 2940 g |
| DCPD | 3696 g |
| Water | 540 g |
| Glycol ether | 254 g |
| Phthalic anhydride | 148 g |
| E51 | 1100 g |
| Vinylbenzene | 6200 g |
Preparing method's step is following:
(1) oleum lini is put in the reaction kettle of 10L, opened stirring, logical nitrogen;
(2) stirring is warming up to 120 ℃, adds catalyzer KOH;
(3) be warming up to 220 ℃, in a small amount of repeatedly tetramethylolmethane input reaction kettle, be warming up to 240 ℃ of insulation reaction again and can clarify at normal temperatures until product with metering;
(4) in the reaction kettle of another 10 L, drop into quantitative MALEIC ANHYDRIDE, the limit adds the waterside heats up, at 60 ~ 80 ℃ of insulation 10 min;
(5) being warming up to 120 ~ 140 ℃, DCPD being dripped into be incubated 2h in the still, is that 190 ~ 230 mgKOH/g finish reaction to acid number;
(6) with glycol ether; Phthalic anhydride, step (3) and step (5) synthetic product are transferred in the 15L reaction kettle, logical nitrogen; Be incubated 1h down at 170 ~ 180 ℃; Continue to be warmed up to 200 ~ 210 ℃ of polycondensations and dehydration again, use resin/vinylbenzene=2/1 preparation sample test bubble pipe viscosity, reaction end is O ~ Q;
(7) above-mentioned resin is cooled to 100 ℃, adds formula ratio E51 and a little catalyzer benzyltriethylammoinium chloride, insulation reaction adds the 200ppm Resorcinol and does stopper to acid number 15 ~ 30mgKOH/g;
(8) resin is under agitation poured into rapidly be equipped with in the cinnamic container, stirring and dissolving is filtered the postcooling cooling and is promptly got said product.
Unsaturated polyester resin application implementation example:
With the resins putty that synthesizes, fill a prescription as follows:
| Title | Consumption (mass parts) |
| Resin | 150 |
| Cobalt iso-octoate | 0.1% resin quality |
| N, accelerine | 0.05% resin quality |
| White titanium pigment | 8.6 |
| Talcum powder | 234 |
| Vinylbenzene | 6 |
The performance index of putty:
| Test item | Technical indicator |
| Air-drying property (25 ℃) | T gel = 8 min，T Polishing= 18 min |
| Grinability | Outstanding (powder delivery is many and fine and smooth) |
| Shock-resistance/cm | 50 |
| Thermotolerance | 180℃ |
| Snappiness/mm | 50 |
| Sticking power/level | 1 |
| Crooked | 50 |
Claims (9)
1. the air-dried unsaturated polyester resin of an excellent combination property; It is characterized in that; It is through transesterify by the affixture of organic polyhydric alcohol, renewable Vegetable oil lipoprotein, DCPD and cis-butenedioic anhydride and small molecules divalent alcohol diprotic acid, epoxy resin; Polycondensation, the polymkeric substance that forms after the ring-opening reaction are dissolved in vinylbenzene and make.
2. the air-dried unsaturated polyester resin of excellent combination property according to claim 1; It is characterized in that; Said organic polyhydric alcohol content is 5.0 ~ 6.0mol, and renewable Vegetable oil lipoprotein content is 2.5 ~ 7.2mol, and the affixture consumption of DCPD and cis-butenedioic anhydride is 15.0 ~ 65.0mol; Each 1.0 ~ 5.0mol of small molecules diprotic acid divalent alcohol, epoxy resin 1.0 ~ 10.0mol.
3. the air-dried unsaturated polyester resin of excellent combination property according to claim 1 is characterized in that, said organic polyhydric alcohol comprises one or more of TriMethylolPropane(TMP), USP Kosher or tetramethylolmethane; Said renewable Vegetable oil lipoprotein comprises tung oil, oleum lini, Oleum Cocois, Semen Maydis oil, Viscotrol C, peanut oil, sunflower seed oil, rapeseed oil, plam oil, soya-bean oil, oil extracted from rice husks etc., one or more in preferred tung oil, oleum lini and the soya-bean oil; Said small molecules divalent alcohol diprotic acid is meant and comprises Ucar 35, glycol ether, terepthaloyl moietie, methyl propanediol, NSC 6366, phthalic anhydride, cis-butenedioic anhydride, hexanodioic acid etc.
4. the preparation method of the air-dried unsaturated polyester resin of an excellent combination property is characterized in that, it may further comprise the steps:
A, transesterification reaction:
The pure and mild renewable Vegetable oil lipoprotein of organic multicomponent is carried out transesterification reaction under certain reaction conditions, catalyzer has one or more in Lithium Hydroxide MonoHydrate, calcium hydroxide, Pottasium Hydroxide, sodium hydroxide, yellow soda ash, sodium hydrogencarbonate or the plumbous oxide;
The preparation of the affixture of B, DCPD and cis-butenedioic anhydride:
In temperature is under 80 ~ 125 ℃, and water and cis-butenedioic anhydride hydrolysis in reactor drum are generated along acid, DCPD is dripped in the into suitable acid again, keeps temperature of reaction between 120 ~ 140 ℃; Or DCPD and cis-butenedioic anhydride mixed in reactor drum, drip water again and generate said affixture;
C, polycondensation:
In the affixture and part small molecules divalent alcohol or the container of diprotic acid with DCPD and cis-butenedioic anhydride by certain reaction conditions adding vegetables oil ester exchange offspring; And have device and whipping appts, and feed nitrogen protection, stir and be warming up to water outlet; 95 ~ 105 ℃ of temperature and 170 ~ 210 ℃ of temperature of reaction are heated up in a steamer in control; To target viscosities, promptly bubble pipe viscosity in resin/vinylbenzene=2/1 time O ~ Q, 150 ℃ of about 10 ± 2 pools of cone-plate;
D, ring-opening reaction:
Epoxy resin and polycondensation product are carried out ring-opening reaction under certain temperature and catalyst action, control stable reaction conditions to target acid number 15 ~ 30mgKOH/g.
E, finished product:
The polymkeric substance that above-mentioned reaction is obtained is dissolved in the air-dried unsaturated polyester resin that vinylbenzene makes excellent combination property.
5. the preparation method of the air-dried unsaturated polyester resin of excellent combination property according to claim 4; It is characterized in that the certain reaction conditions in the said steps A refers to that the molar ratio of the pure and mild renewable Vegetable oil lipoprotein of organic multicomponent is 1:0.5 ~ 1:1.2,180 ~ 240 ℃ of temperature of reaction; Nitrogen protection; The preferred Lithium Hydroxide MonoHydrate of catalyzer, reaction detects patience with product and methyl alcohol volume ratio 1/3, and clarifying no phase-splitting is terminal point.
6. the preparation method of the air-dried unsaturated polyester resin of excellent combination property according to claim 4 is characterized in that, the certain reaction conditions among the said step C refers to that DCPD and cis-butenedioic anhydride affixture and ester exchange offspring are 1:0.2 ~ 1:0.5 in molar ratio; Heat up in a steamer 95 ~ 105 ℃ of temperature; 170 ~ 210 ℃ of temperature of reaction are used resin/vinylbenzene=2/1 preparation sample, with bubble pipe viscosity or cone-and-plate viscometer controlled target value; Reaction end is O ~ Q, 150 ℃ of about 10 ± 2 pools of cone-plate.
7. the preparation method of the air-dried unsaturated polyester resin of excellent combination property according to claim 4 is characterized in that, the epoxy resin among the said step D is one or more mixtures of E55, E51, E44, E42, E35.
8. the preparation method of the air-dried unsaturated polyester resin of excellent combination property according to claim 4 is characterized in that, the certain temperature among the said step D refers to that temperature of reaction is 90 ~ 130 ℃.
9. the preparation method of the air-dried unsaturated polyester resin of excellent combination property according to claim 4; It is characterized in that; Catalyzer among the said step D is quaternary ammonium salt, tertiary ammonium salt, alkali, salt, like benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, N, accelerine, benzyldimethylamine, benzyl diethylamine, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetramethyl ammonium chloride, 4 bromide, tetraphenylphosphonibromide bromide and catalyzer benzyltriethylammoinium chloride.
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| CN102766252A (en) * | 2012-06-27 | 2012-11-07 | 淄博德信联邦化学工业有限公司 | Preparation method of vegetable oil polyester polyol for preparing rigid polyurethane foam |
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