CN105085885A - Colorant matrix resin for unsaturated polyester resin and preparation method thereof - Google Patents
Colorant matrix resin for unsaturated polyester resin and preparation method thereof Download PDFInfo
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Abstract
The invention particularly discloses colorant matrix resin for unsaturated polyester resin and a preparation method thereof. The colorant matrix resin is formed by conducting copolymerization on acid, dihydric alcohol and auxiliaries, wherein the acid comprises unsaturated acid and saturated acid, the molar ratio of the unsaturated acid to the saturated acid is 0.1-1 to 1, the dihydric alcohol comprises polyethylene glycol, the polyethylene glycol accounts for 1%-50% of the total mass of addition of synthesis materials, the molecular weight of the polyethylene glycol ranges from 200 to 2,000, and the molar ratio of the dihydric alcohol to the acid is 1-5 to 1. According to the colorant matrix resin for the unsaturated polyester resin and the preparation method thereof, due to the fact that polyethylene glycol with different molecular weights and different mass fractions is selected, the viscosity modulation factor of the colorant matrix resin is greatly increased, the compatibility of an organic molecular chain and an inorganic substance is improved, the compatibility of the colorant matrix resin and inorganic color powder and the wettability of the colorant matrix resin and inorganic filler are promoted, the compatibility of the colorant matrix resin and unsaturated polyester is improved, and the tinting strength of the colorant matrix resin and a product and the capacity of resisting discoloration in the later using process of a finished product of unsaturated polyester resin are greatly improved.
Description
Technical field
The present invention relates to unsaturated polyester resin technical field, particularly relate to a kind of unsaturated polyester resin mill base matrix resin and preparation method thereof.
Background technology
Unsaturated polyester resin is one the most frequently used in thermosetting resin, formed by unsaturated dibasic acid dibasic alcohol or the unsaturated dibasic alcohol polycondensation of monounsaturated dicarboxylic acid, through the resin solution with certain viscosity that cross-linking monomer or strong solvent dilution are formed, be the chain macromolecule compound with ester bond and unsaturated double-bond, be called for short UPR.
Along with unsaturated polyester resin product-use is more and more wide, people require also more and more stricter to the color of its goods.Traditional painted be utilize pigment powder to be directly added in unsaturated polyester resin, then solidification is made goods and is carried out painted.Do like this and there is certain drawback: the circulation ratio as color is bad, painted uneven, owing to there is no technology and the technique of specialty, granules of pigments is relatively thicker, and tinting strength is not high, seriously polluted, be added in coating, photostabilization after coating film forming, weather resisteant are poor, easily fade, efflorescence etc.So mill base arises.
The main production process of mill base is uniformly mixed in advance color powder and matrix resin, then makes mill base finished product by shredder grinding.The tinting strength of mill base and mill base all have greatly improved mutually than before in the dispersiveness of unsaturated polyester book and consistency, moreover, relatively traditional is painted, and mill base has excellent performance in anti-aging, weathering resistance, the photostabilization in the goods later stage of unsaturated polyester resin.Therefore, mill base not only claims to pigment powder, proposes higher requirement for participating in grinding and occupying a high proportion of matrix resin.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of unsaturated polyester resin mill base matrix resin, and the viscosity modulation factor of amplitude modulation of mill base matrix resin is improved greatly.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of unsaturated polyester resin mill base matrix resin, is synthesized by following material copolymerization: acid, dibasic alcohol and auxiliary agent; Wherein, described acid comprises unsaturated acid and saturated acid, and the mol ratio of unsaturated acid and saturated acid is (0.1 ~ 1): 1; Described dibasic alcohol comprise account for synthesis material add total mass 1% ~ 50%, molecular weight is the polyoxyethylene glycol of 200 ~ 2000, described dibasic alcohol is (1 ~ 5) with the mol ratio of acid: 1; Described auxiliary agent comprises oxidation inhibitor and stopper.
Preferably, the addition of described oxidation inhibitor is that synthesis material adds 0.5 ‰ ~ 1.5 ‰ of total mass, and the addition of described stopper is the 10ppm-200ppm that synthesis material adds total mass.
The present invention also provides a kind of preparation method of unsaturated polyester resin mill base matrix resin, and concrete steps are:
1). take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2). in reactor, drop into acid by the order of first throw liq material, rear throwing solid material, comprise the dibasic alcohol of polyoxyethylene glycol and appropriate stopper and oxidation inhibitor, be warming up to 130 DEG C ~ about 140 DEG C, in reactor, pass into nitrogen, horizontal condenser supplies water;
3). when temperature of charge rises to 150 DEG C ~ 155 DEG C, open stirrer, stir speed (S.S.) is 50 ~ 55 revs/min;
4). when fractionation tower temperature rises to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5). when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 25 ~ 45mgKOH/g to acid number, again pass into nitrogen;
6). vacuumize continuation reaction and stop when acid number is 15 ~ 35mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds appropriate stopper, then continue to be cooled to less than 50 DEG C, close water coolant and also stop stirring, packaging.
In present method invention, in this step 2) in add appropriate stopper and antioxidant be to prevent from building-up process, because the amount of unsaturated acid is too large, temperature of reaction is too high and cause knot still, ensureing well carrying out smoothly of building-up reactions; In this step 6) in add appropriate stopper again effect comprise and make the stability in storage of mill base matrix resin finished product higher.The add-on of described stopper is determined according to the category of dibasic alcohol and acid and addition, adds at twice, step 2) in stopper add-on be generally 1/3 ~ 1/2 of stopper total addition level.
Preferably, above-mentioned steps 2) and step 5) in flow of nitrogen gas speed be 0.5m
3/ h.
Preferably, described dibasic alcohol also comprises one or more mixtures in ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, Hydrogenated Bisphenol A, neopentyl glycol, methyl propanediol.
Preferably, described unsaturated acid is one or more mixtures in MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, FUMARIC ACID TECH GRADE, maleic acid.
Preferably, described saturated acid is that chloro is along one or more mixtures in butyric acid, m-phthalic acid, terephthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid, sebacic acid, tetrachlorophthalic anhydride, phenylformic acid.
Preferably, described stopper is one or more mixtures in Resorcinol, toluhydroquinone, p-ten.-butylcatechol.
Preferably, described oxidation inhibitor is ditert-butylhydro quinone and/or triphenyl phosphite.
The beneficial effect that the present invention compared with prior art has: the present invention is by adding polyoxyethylene glycol synthesis mill base matrix resin, because the molecular weight alternative of polyoxyethylene glycol is wider, the present invention, by the molecular size range selecting the polyoxyethylene glycol of different molecular weight and interpolation different mass mark to control synthesizing polyester, makes the viscosity modulation factor of amplitude modulation of required mill base matrix resin greatly improve.Again due to the existence of ehter bond in polyoxyethylene glycol, improve the consistency of organic molecule chain and inorganics, the present invention is by adding polyoxyethylene glycol, improve the consistency of itself and inorganic color powder to a certain extent, in later stage use procedure, also improve the wetting property of the inorganic fillings such as itself and glass fibre to a certain extent.Again due to the existence of polyoxyethylene glycol two terminal hydroxy group, participate in producing ester group with the esterification of acid in building-up process, improve the consistency of itself and unsaturated polyester, and due to the existence of unsaturated acid in molecular chain, make it use in solidification process in the later stage and participate in double bond crosslinking reaction, increase substantially the anti-decoloring ability in the tinting strength of itself and goods and the later stage use procedure of unsaturated polyester resin finished product.Because the polyester molecule chain of polyoxyethylene glycol and formation all belongs to high boiling substance, this matrix resin is tasteless at normal temperatures, and with toner process of lapping in highly stablely can not decompose generation toxic and harmful, safety and environmental protection.
Embodiment
Embodiment one:
The matrix resin of the present embodiment one is synthesized by following material copolymerization: (in the present embodiment, dibasic alcohol is 2.26:1 with the mol ratio of acid for neopentyl glycol 1600Kg, propylene glycol 300Kg, Tetra hydro Phthalic anhydride 800Kg, MALEIC ANHYDRIDE 300Kg, Resorcinol 150g, 200 molecular weight polyethylene glycol 130Kg, triphenyl phosphite 3Kg; The mol ratio of unsaturated acid and saturated acid is 0.57:1, and polyoxyethylene glycol addition is 4.1%), concrete preparation method is as follows:
1) take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2) in reactor, neopentyl glycol, the propylene glycol of 300Kg, the Tetra hydro Phthalic anhydride of 800Kg, the MALEIC ANHYDRIDE of 300Kg, the polyoxyethylene glycol of 130Kg, the triphenyl phosphite of 3Kg, the Resorcinol of 75g of 1600Kg is dropped into by the order of first throw liq material, rear throwing solid material, be warming up to 140 DEG C, in reactor, pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h, horizontal condenser supplies water;
3) when temperature of charge rises to 155 DEG C, open stirrer, stir speed (S.S.) is 50 revs/min;
4) when fractionation tower temperature to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5) when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 30mgKOH/g to acid number, again pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h;
6) vacuumize continuation reaction to stop when acid number is 20mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds the Resorcinol of remaining 75g, then continue to be cooled to less than 50 DEG C, close water coolant and also stop stirring, packaging.
Embodiment two:
The matrix resin of the present embodiment two is synthesized by following material copolymerization: the polyoxyethylene glycol 250Kg of methyl propanediol 1100Kg, hexanodioic acid 800Kg, MALEIC ANHYDRIDE 500Kg, 600 molecular weight, (in the present embodiment, dibasic alcohol is 1.57:1 with the mol ratio of acid for Resorcinol 150g, triphenyl phosphite 2.5Kg; The mol ratio of unsaturated acid and saturated acid is 0.93:1, and polyoxyethylene glycol addition is 10.3%), concrete preparation method is as follows:
1) take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2) in reactor, methyl propanediol, the MALEIC ANHYDRIDE of 500Kg, the hexanodioic acid of 800Kg, the polyoxyethylene glycol of 250Kg, the triphenyl phosphite of 2.5Kg, the Resorcinol of 75g of 1100Kg is dropped into by the order of first throw liq material, rear throwing solid material, be warming up to 130 DEG C, in reactor, pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h, horizontal condenser supplies water;
3) when temperature of charge rises to 150 DEG C, open stirrer, stir speed (S.S.) is 50 revs/min;
4) when fractionation tower temperature to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5) when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 40mgKOH/g to acid number, again pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h;
6) vacuumize continuation reaction to stop when acid number is 30mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds the Resorcinol of remaining 75g, then continue to be cooled to less than 50 DEG C, close water coolant and also stop stirring, packaging.
Embodiment three:
The matrix resin of the present embodiment three is synthesized by following material copolymerization: ethylene glycol 400Kg, propylene glycol 500Kg, Tetra hydro Phthalic anhydride 900Kg, MALEIC ANHYDRIDE 400Kg, 800 molecular weight polyethylene glycol 575Kg, (in the present embodiment, dibasic alcohol is 1.28:1 with the mol ratio of acid for triphenyl phosphite 2.5Kg, Resorcinol 150g; The mol ratio of unsaturated acid and saturated acid is 0.67:1, and polyoxyethylene glycol addition is 20.7%), concrete preparation method is as follows:
1) take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2) in reactor, ethylene glycol, the propylene glycol of 500Kg, the Tetra hydro Phthalic anhydride of 900Kg, the MALEIC ANHYDRIDE of 400Kg, the polyoxyethylene glycol of 575Kg, the triphenyl phosphite of 2.5Kg, the Resorcinol of 75g of 400Kg is dropped into by the order of first throw liq material, rear throwing solid material, be warming up to 140 DEG C, in reactor, pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h, horizontal condenser supplies water;
3) when temperature of charge rises to 150 DEG C, open stirrer, stir speed (S.S.) is 50 revs/min;
4) when fractionation tower temperature to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5) when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 35mgKOH/g to acid number, again pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h;
6) vacuumize continuation reaction to stop when acid number is 23mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds the Resorcinol of remaining 75g, then continue to be cooled to less than 50 DEG C, close water coolant and also stop stirring, packaging.
Embodiment four:
The matrix resin of the present embodiment four is synthesized by following material copolymerization: (in the present embodiment, dibasic alcohol is 1.31:1 with the mol ratio of acid for Polyethylene Glycol-600 Kg, the triphenyl phosphite 4Kg of glycol ether 800Kg, neopentyl glycol 300Kg, methyl propanediol 400Kg, phenylformic acid 200Kg, m-phthalic acid 900Kg, FUMARIC ACID TECH GRADE acid anhydride 500Kg, 200 molecular weight, Resorcinol 150g; The mol ratio of unsaturated acid and saturated acid is 0.79:1, and polyoxyethylene glycol addition is 16.2%), concrete preparation method is as follows:
1) take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2) in reactor, glycol ether, the neopentyl glycol of 300Kg, the methyl propanediol of 400Kg, the phenylformic acid of 200Kg, the m-phthalic acid of 900Kg, the FUMARIC ACID TECH GRADE acid anhydride of 500Kg, the polyoxyethylene glycol of 600Kg, the triphenyl phosphite of 4Kg, the Resorcinol of 75g of 800Kg is dropped into by the order of first throw liq material, rear throwing solid material, be warming up to 140 DEG C, in reactor, pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h, horizontal condenser supplies water;
3) when temperature of charge rises to 152 DEG C, open stirrer, stir speed (S.S.) is 55 revs/min;
4) when fractionation tower temperature to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5) when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 33mgKOH/g to acid number, again pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h;
6) vacuumize continuation reaction to stop when acid number is 25mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds the Resorcinol of remaining 75g, then continue to be cooled to less than 50 DEG C, close water coolant and also stop stirring, packaging.
Embodiment five:
The matrix resin of the present embodiment five is synthesized by following material copolymerization: (in the present embodiment, dibasic alcohol is 1.17:1 with the mol ratio of acid for polyethylene glycol-800 Kg, the ditert-butylhydro quinone 3.5Kg of dipropylene glycol 800Kg, neopentyl glycol 300Kg, phenylformic acid 200Kg, SA 900Kg, FUMARIC ACID TECH GRADE 400Kg, 1000 molecular weight, Resorcinol 100g, toluhydroquinone 100g; The mol ratio of unsaturated acid and saturated acid is 0.77:1, and polyoxyethylene glycol addition is 23.5%), concrete preparation method is as follows:
1) take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2) in reactor, dipropylene glycol, the neopentyl glycol of 300Kg, the phenylformic acid of 200Kg, the SA of 900Kg, the FUMARIC ACID TECH GRADE acid anhydride of 400Kg, the polyoxyethylene glycol of 800Kg, the ditert-butylhydro quinone of 3.5Kg, the Resorcinol of 50g, the toluhydroquinone of 50g of 800Kg is dropped into by the order of first throw liq material, rear throwing solid material, be warming up to 135 DEG C, in reactor, pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h, horizontal condenser supplies water;
3) when temperature of charge rises to 152 DEG C, open stirrer, stir speed (S.S.) is 53 revs/min;
4) when fractionation tower temperature to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5) when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 33mgKOH/g to acid number, again pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h;
6) vacuumize continuation reaction to stop when acid number is 25mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds the Resorcinol of remaining 50g, the toluhydroquinone of 50g, then continue to be cooled to less than 50 DEG C, close water coolant and stop stirring, packaging.
Embodiment six:
The matrix resin of the present embodiment six is synthesized by following material copolymerization: (in the present embodiment, dibasic alcohol is 1.78:1 with the mol ratio of acid for polyoxyethylene glycol 1100Kg, the ditert-butylhydro quinone 3.5Kg of dipropylene glycol 500Kg, ethylene glycol 300Kg, methyl propanediol 400Kg, terephthalic acid 200Kg, Tetra hydro Phthalic anhydride 500Kg, MALEIC ANHYDRIDE 300Kg, 1500 molecular weight, Resorcinol 100g, p-ten.-butylcatechol 100g; The mol ratio of unsaturated acid and saturated acid is 0.66:1, and polyoxyethylene glycol addition is 33.3%), concrete preparation method is as follows:
1) take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2) in reactor, dipropylene glycol, the ethylene glycol of 300Kg, the methyl propanediol of 400Kg, the terephthalic acid of 200Kg, the Tetra hydro Phthalic anhydride of 500Kg, the MALEIC ANHYDRIDE of 300Kg, the polyoxyethylene glycol of 1100Kg, the ditert-butylhydro quinone of 3.5Kg, the Resorcinol of 50g, the p-ten.-butylcatechol of 50g of 500Kg is dropped into by the order of first throw liq material, rear throwing solid material, be warming up to 140 DEG C, in reactor, pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h, horizontal condenser supplies water;
3) when temperature of charge rises to 155 DEG C, open stirrer, stir speed (S.S.) is 50 revs/min;
4) when fractionation tower temperature to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5) when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 35mgKOH/g to acid number, again pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h;
6) vacuumize continuation reaction to stop when acid number is 23mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds the Resorcinol of remaining 50g, the p-ten.-butylcatechol of 50g, then continue to be cooled to less than 50 DEG C, close water coolant and stop stirring, packaging.
Embodiment seven:
The matrix resin of the present embodiment seven is synthesized by following material copolymerization: (in the present embodiment, dibasic alcohol is 1.58:1 with the mol ratio of acid for polyethylene glycol 1500 Kg, the ditert-butylhydro quinone 3.5Kg of Hydrogenated Bisphenol A 300Kg, propylene glycol 600Kg, tetrachlorophthalic anhydride 200Kg, m-phthalic acid 500Kg, maleic acid 300Kg, 1000 molecular weight, toluhydroquinone 150g; The mol ratio of unsaturated acid and saturated acid is 0.82:1, and polyoxyethylene glycol addition is 44.1%), concrete preparation method is as follows:
1) take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2) in reactor, Hydrogenated Bisphenol A, the propylene glycol of 600Kg, the tetrachlorophthalic anhydride of 200Kg, the m-phthalic acid of 500Kg, the maleic acid of 300Kg, the polyoxyethylene glycol of 1500Kg, the ditert-butylhydro quinone of 3.5Kg, the toluhydroquinone of 75g of 300Kg is dropped into by the order of first throw liq material, rear throwing solid material, be warming up to 135 DEG C, in reactor, pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h, horizontal condenser supplies water;
3) when temperature of charge rises to 150 DEG C, open stirrer, stir speed (S.S.) is 55 revs/min;
4) when fractionation tower temperature to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5) when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 37mgKOH/g to acid number, again pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h;
6) vacuumize continuation reaction to stop when acid number is 25mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds the toluhydroquinone of remaining 75g, then continue to be cooled to less than 50 DEG C, close water coolant and also stop stirring, packaging.
Embodiment eight:
The matrix resin of the present embodiment eight is synthesized by following material copolymerization: (in the present embodiment, dibasic alcohol is 1.18:1 with the mol ratio of acid for cetomacrogol 1000 Kg, the ditert-butylhydro quinone 3.5Kg of Hydrogenated Bisphenol A 300Kg, neopentyl glycol 500Kg, glycol ether 500Kg, tetrachlorophthalic anhydride 200Kg, hexanodioic acid 600Kg, MALEIC ANHYDRIDE 300Kg, 2000 molecular weight, p-ten.-butylcatechol 80g, toluhydroquinone 100g; The mol ratio of unsaturated acid and saturated acid is 0.47:1, and polyoxyethylene glycol addition is 29.4%), concrete preparation method is as follows:
1) take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2) in reactor, glycol ether, the neopentyl glycol of 500Kg, the Hydrogenated Bisphenol A of 300Kg, the tetrachlorophthalic anhydride of 200Kg, the hexanodioic acid of 600Kg, the MALEIC ANHYDRIDE of 300Kg, the polyoxyethylene glycol of 1000Kg, the ditert-butylhydro quinone of 3.5Kg, the toluhydroquinone of 50g, the p-ten.-butylcatechol of 50g of 500Kg is dropped into by the order of first throw liq material, rear throwing solid material, be warming up to 140 DEG C, in reactor, pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h, horizontal condenser supplies water;
3) when temperature of charge rises to 155 DEG C, open stirrer, stir speed (S.S.) is 55 revs/min;
4) when fractionation tower temperature to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5) when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 30mgKOH/g to acid number, again pass into nitrogen, the flow rate of described nitrogen is 0.5m
3/ h;
6) vacuumize continuation reaction to stop when acid number is 18mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds the toluhydroquinone of remaining 50g, the p-ten.-butylcatechol of 30g, then continue to be cooled to less than 50 DEG C, close water coolant and stop stirring, packaging.
The quality product detected result that the various embodiments described above obtain is as follows:
| Test item | Outward appearance | Acid number (mgKOH/g) | Viscosity (mPa.s) |
| Detection method | Range estimation | GB/T2895 | GB/T7193.1 |
| Embodiment one | Light yellow clear | 20 | 500 |
| Embodiment two | Water white is transparent | 30 | 1300 |
| Embodiment three | Light yellow clear | 23 | 3000 |
| Embodiment four | Light yellow clear | 25 | 800 |
| Embodiment five | Light yellow clear | 25 | 4050 |
| Embodiment six | Light yellow clear | 23 | 2600 |
| Embodiment seven | Water white is transparent | 25 | 1900 |
| Embodiment eight | Water white is transparent | 18 | 4500 |
The present invention is not limited to above-mentioned preferred forms, and anyone should learn the structural changes made under enlightenment of the present invention, and every have identical or close technical scheme with the present invention, all falls within protection scope of the present invention.
Claims (9)
1. a unsaturated polyester resin mill base matrix resin, is characterized in that,
This matrix resin is synthesized by following material copolymerization: acid, dibasic alcohol and auxiliary agent; Wherein,
Described acid comprises unsaturated acid and saturated acid, and the mol ratio of unsaturated acid and saturated acid is (0.1 ~ 1): 1;
Described dibasic alcohol comprise account for synthesis material add total mass 1% ~ 50%, molecular weight is the polyoxyethylene glycol of 200 ~ 2000, described dibasic alcohol is (1 ~ 5) with the mol ratio of acid: 1;
Described auxiliary agent comprises oxidation inhibitor and stopper.
2. unsaturated polyester resin mill base matrix resin according to claim 1, it is characterized in that, described dibasic alcohol also comprises one or more mixtures in ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, Hydrogenated Bisphenol A, neopentyl glycol, methyl propanediol.
3. unsaturated polyester resin mill base matrix resin according to claim 1, is characterized in that, described unsaturated acid is one or more mixtures in MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, FUMARIC ACID TECH GRADE, maleic acid.
4. unsaturated polyester resin mill base matrix resin according to claim 1, it is characterized in that, described saturated acid is that chloro is along one or more mixtures in butyric acid, m-phthalic acid, terephthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid, sebacic acid, tetrachlorophthalic anhydride, phenylformic acid.
5. unsaturated polyester resin mill base matrix resin according to claim 1, is characterized in that, described stopper is one or more mixtures in Resorcinol, toluhydroquinone, p-ten.-butylcatechol.
6. unsaturated polyester resin mill base matrix resin according to claim 1, is characterized in that, described oxidation inhibitor is ditert-butylhydro quinone and/or triphenyl phosphite.
7. the mill base matrix resin of the unsaturated polyester resin according to any one of claim 1 to 6, it is characterized in that, the addition of described oxidation inhibitor is that synthesis material adds 0.5 ‰ ~ 1.5 ‰ of total mass, and the addition of described stopper is the 10ppm-200ppm that synthesis material adds total mass.
8. the preparation method for mill base matrix resin of the unsaturated polyester resin as described in any one of claim 1 to 7, is characterized in that, concrete steps are:
1). take each synthesis material component by weight ratio, whether normally review and validate equipment, electrical equipment, instrument, valve and starting material;
2). in reactor, drop into acid by the order of first throw liq material, rear throwing solid material, comprise the dibasic alcohol of polyoxyethylene glycol and appropriate stopper and oxidation inhibitor, be warming up to 130 DEG C ~ about 140 DEG C, in reactor, pass into nitrogen, horizontal condenser supplies water;
3). when temperature of charge rises to 150 DEG C ~ 155 DEG C, open stirrer, stir speed (S.S.) is 50 ~ 55 revs/min;
4). when fractionation tower temperature rises to 102 DEG C, adopt vertical (type) condenser to supply water, stop passing into nitrogen, and to control fractionation tower temperature be 100 DEG C ~ 103 DEG C;
5). when temperature of charge rises to 205 DEG C, control temperature of reaction and continue insulation reaction in 205 DEG C ~ 208 DEG C, when reaction is 25 ~ 45mgKOH/g to acid number, again pass into nitrogen;
6). vacuumize continuation reaction and stop to during acid number 15 ~ 35mgKOH/g, then lower the temperature, after temperature of reaction is down to 190 DEG C, adds appropriate stopper, then continue to be cooled to less than 50 DEG C, close water coolant and also stop stirring, packaging.
9. the preparation method of unsaturated polyester resin mill base matrix resin according to claim 8, is characterized in that, above-mentioned steps 2) and step 5) in flow of nitrogen gas speed be 0.5m
3/ h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510603110.1A CN105085885A (en) | 2015-09-21 | 2015-09-21 | Colorant matrix resin for unsaturated polyester resin and preparation method thereof |
Applications Claiming Priority (1)
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| CN105440622A (en) * | 2015-12-20 | 2016-03-30 | 福建梭罗复合材料研究有限公司 | Gel coat with high thixotropic property and low viscosity and preparation method thereof |
| CN105482087A (en) * | 2015-12-28 | 2016-04-13 | 肇庆福田化学工业有限公司 | Anti-yellowing unsaturated polyester resin and synthetic method thereof |
| CN105566619A (en) * | 2016-03-02 | 2016-05-11 | 永悦科技股份有限公司 | Method for synthesizing novel high-efficiency thixotropic marine resin |
| CN105647097A (en) * | 2016-04-12 | 2016-06-08 | 无锡南理工科技发展有限公司 | Flame-retardant resin |
| CN105647141A (en) * | 2016-04-12 | 2016-06-08 | 无锡南理工科技发展有限公司 | Preparation method of flame-retardant resin |
| CN109575258A (en) * | 2018-11-27 | 2019-04-05 | 镇江利德尔复合材料有限公司 | A kind of preparation method for the vector resin that refractory molded technique coloured material uses |
| CN110054757A (en) * | 2019-04-26 | 2019-07-26 | 永悦科技股份有限公司 | A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin |
| CN110903472A (en) * | 2018-09-15 | 2020-03-24 | 福建省南安市华龙树脂有限公司 | Preparation method of polyester for low-viscosity color paste matrix |
| CN111621129A (en) * | 2020-06-02 | 2020-09-04 | 山东凯威尔新材料有限公司 | High-weather-resistance polyester resin and preparation method thereof |
| CN113087853A (en) * | 2021-04-26 | 2021-07-09 | 宜兴市兴合树脂有限公司 | Pultrusion resin for producing frame structure for shallow sea cultivation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105440622A (en) * | 2015-12-20 | 2016-03-30 | 福建梭罗复合材料研究有限公司 | Gel coat with high thixotropic property and low viscosity and preparation method thereof |
| CN105482087A (en) * | 2015-12-28 | 2016-04-13 | 肇庆福田化学工业有限公司 | Anti-yellowing unsaturated polyester resin and synthetic method thereof |
| CN105566619A (en) * | 2016-03-02 | 2016-05-11 | 永悦科技股份有限公司 | Method for synthesizing novel high-efficiency thixotropic marine resin |
| CN105647097A (en) * | 2016-04-12 | 2016-06-08 | 无锡南理工科技发展有限公司 | Flame-retardant resin |
| CN105647141A (en) * | 2016-04-12 | 2016-06-08 | 无锡南理工科技发展有限公司 | Preparation method of flame-retardant resin |
| CN110903472A (en) * | 2018-09-15 | 2020-03-24 | 福建省南安市华龙树脂有限公司 | Preparation method of polyester for low-viscosity color paste matrix |
| CN109575258A (en) * | 2018-11-27 | 2019-04-05 | 镇江利德尔复合材料有限公司 | A kind of preparation method for the vector resin that refractory molded technique coloured material uses |
| CN110054757A (en) * | 2019-04-26 | 2019-07-26 | 永悦科技股份有限公司 | A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin |
| CN111621129A (en) * | 2020-06-02 | 2020-09-04 | 山东凯威尔新材料有限公司 | High-weather-resistance polyester resin and preparation method thereof |
| CN113087853A (en) * | 2021-04-26 | 2021-07-09 | 宜兴市兴合树脂有限公司 | Pultrusion resin for producing frame structure for shallow sea cultivation |
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