CN101633729B - Method for preparing unsaturated polyster resin by industrial dicyclopentadiene - Google Patents
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Abstract
The invention relates to a method for preparing an unsaturated polyster resin by industrial dicyclopentadiene. In the method, dicyclopentadiene and water are firstly added into a reaction system; unsaturated dicarboxylic anhydrides are added by dropping to carry out addition reaction under a thermal insulation state; then dihydric alcohol and dicarboxylic acid (or anhydride) are added to carry out polycondensation; and finally, after a polymerization inhibitor is added, vinyl crosslinking monomer is poured, and an unsaturated polyster resin product can be obtained after uniform mixing. The adopted method has low purity requirement to the dicyclopentadiene, low production cost, stable process conditions and production equipment which can be commonly used with equipment of the prior art, and a catalyst is not needed in a reaction process. The industrial dicyclopentadiene modified unsaturated polyster resin has the advantages of heat resistance, water resistance, chemical corrosion resistance, air-drying property, low contractility, and the like, has light resin color of light yellow and product chroma smaller than or equal to Gardner color code No.3, and can be applied to manufacture of a light colored product.
Description
Technical field
The present invention relates to field of polymer material preparing technology, relate in particular to a kind of method of preparing unsaturated polyster resin by industrial dicyclopentadiene.
Background technology
Unsaturated polyester resin is that diprotic acid and dibasic alcohol polycondensation form polymkeric substance, contains the unsaturated link(age) of non-aromatics in its molecular structure, and available suitable initiator causes the linking agent reaction and becomes a kind of thermosetting resin.Dicyclic pentylene modified unsaturated polyester resin has characteristics such as thermotolerance, water tolerance, chemical resistance, air-drying property and low-shrinkage, has been widely used in various fields such as glass fibre reinforcement, chemical anticorrosion, sanitary ware, artwork manufacturing.Along with socioeconomic fast development, the market demand of unsaturated polyester resin is increased year by year, the unsaturated polyester resin of therefore developing property satisfies economic construction has become the task of top priority.
Dicyclopentadiene is mainly derived from the by product C of petroleum cracking system ethylene industry
5In cut and the coal tar,, be the raw material of petroleum resin and multiple fine chemicals because chemical property is active.Have now found that, the unsaturated polyester resin that by dicyclopentadiene is material modification all is greatly enhanced at aspects such as thermotolerance, water tolerance, chemical resistance and air-drying properties, and dcpd resin has become one of principal item of modified unsaturated polyester resin.And dicyclopentadiene is abundant as ethylene industry by product source, and the research that therefore utilizes the dicyclopentadiene of domestic abundant raw material to prepare modified unsaturated polyester resin has caused extensive concern.
The main method of preparation dicyclic pentylene modified unsaturated polyester resin has acid anhydrides method, half esterification process, hydrolysis method, blocking method etc. both at home and abroad at present.Wherein be to prepare the common method of dicyclic pentylene modified unsaturated polyester resin with the hydrolysis method.Chinese patent CN101153072A disclosed " method that is prepared modified unsaturated polyester resin by technical grade dicyclopentadiene " has introduced with unsaturated or monounsaturated dicarboxylic acid or acid anhydrides and mixed C
5Separating the technical grade dicyclopentadiene that obtains in the cut is raw material, drip distilled water to it, after the hydrolysis addition reaction, add an amount of dibasic alcohol or polyvalent alcohol again, under an acidic catalyst effect, carry out the polycondensation dehydration, the color of the dicyclic pentylene modified unsaturated polyester resin that this inventive method obtains is a sundown, Gardner's colourity is higher, is not suitable for to make light goods, as making such as light rostone, light coatings.
Chinese patent CN1880358A disclosed " preparation method of dicyclic pentylene modified unsaturated polyester resin " has introduced with unsaturated dicarboxylic acid anhydride, water and dicyclopentadiene and carried out the DCPA that addition reaction obtains unsaturated dibasic acid under catalyzer.Catalyzer is the composition to phosphoric acid and toluene sulfonic acide.The mixture that adds dibasic alcohol and trivalent alcohol in the reactant system carries out polycondensation, finishes reaction after less than 50mgKOH/g to the acid number of reactant, removes the water of generation in the reaction process; Reactant is cooled to 100～110 ℃, adds vinyl cross-linking monomer diluting reaction thing and adds stopper, promptly gets the dicyclic pentylene modified unsaturated polyester resin product after mixing.Product of the present invention is light yellow, transparent liquid.But the composition of catalyzer phosphoric acid and toluene sulfonic acide add the gel time that affiliation influences easily resin, influence the performance of goods.Simultaneously also can improve production cost.
For making resin obtain good color and luster, all adopting " polyester grade " dicyclopentadiene abroad is that raw material (purity is more than 93%) is produced dicyclic pentylene modified unsaturated polyester by hydrolysis method, and product is a yellow transparent liquid.But, be not suitable for the suitability for industrialized production dicyclic pentylene modified unsaturated polyester resin because the price of the high purity dicyclo pentylene that market provided is too high.
And light goods are indispensable in social production life, and the synthetic method that therefore, cost of development is low, light, possess the dicyclic pentylene modified unsaturated polyester resin excellent properties simultaneously has very big market outlook.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method of preparing unsaturated polyster resin by industrial dicyclopentadiene, this method is low to the purity requirement of dicyclopentadiene, production cost is low, good in economic efficiency, and the unsaturated polyester resin color that obtains is light yellow, is applicable to the making of light goods.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A, in the four-hole container that nitrogen protection, agitator, thermometer, fractional column device are housed, add mol ratio and be 1: 1～1: 2 technical grade dicyclopentadiene and water, be warming up to 80～150 ℃, drip unsaturated dicarboxylic acid anhydride; Dropwise the back in 100～150 ℃ of insulations, continue to react to acid number be 190～290mgKOH/g;
B, the mixture that continues to add dibasic alcohol in the four-hole container or add dibasic alcohol and diprotic acid or acid anhydrides are warming up to 160～205 ℃, carry out the polycondensation dehydration reaction, to acid number be smaller or equal to 50mgKOH/g;
C, reactant is cooled to 110～180 ℃, after add-on is the 200mg/kg Resorcinol stopper of resin total amount, pouring volume is the 30% vinylbenzene cross-linking monomer dilution of resin total amount, promptly gets the light unsaturated polyester resin of technical grade dicyclopentadiene preparation after mixing.
As limitation of the invention further, the purity of described dicyclopentadiene is 78～85wt%.
The colourity of described unsaturated polyester resin is tested by GB/T22295-2008 color of transparent liquids measuring method, and its colourity is smaller or equal to No. 3, Gardner color scale.
In addition, the unsaturated dicarboxylic acid anhydride described in the step a of the present invention is: MALEIC ANHYDRIDE, the mol ratio of MALEIC ANHYDRIDE and dicyclopentadiene 2: 1～1: 1; Dibasic alcohol described in the step b is ethylene glycol, propylene glycol, neopentyl glycol, glycol ether, dipropylene glycol, propoxylated bisphenol, 1,4-butyleneglycol, 2,3-butyleneglycol etc.; Described diprotic acid or acid anhydrides are: Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, hexanodioic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, tetrahydrophthalic anhydride, Succinic Acid, pentanedioic acid, pimelic acid, the special acid in sea, PHT4, tetrachlorophthalic anhydride etc.
Key of the present invention be each raw material in step a order of addition(of ingredients) unlike the prior art, prior art drips water or dicyclopentadiene usually in MALEIC ANHYDRIDE, as patent CN 1056388C, CN1880358A, method described in the CN 101153072A, and reaction system of the present invention is to drop into dicyclopentadiene and water earlier, drip MALEIC ANHYDRIDE then, carry out addition reaction again, significantly reduced the side reaction generation, and because the improvement of technology makes that not using catalyzer in reaction process is that availability is good, color is lurid unsaturated polyester resin product, the colourity of this product is smaller or equal to No. 3, Gardner color scale, and it is good to have resistance toheat simultaneously, water-fast, resistance to chemical corrosion is good, characteristics such as air-drying property and low-shrinkage.In addition, the product of gained of the present invention can be applicable to light goods and makes, has very vast market prospect, compare with prior art, solve technical grade dicyclopentadiene greatly and prepared the darker problem of unsaturated polyester resin color, and in entire reaction course, do not need to use catalyzer, saved cost, and production unit can be also general with prior art equipment.Our company is successful mass production more than ten batches at present, and obtains client's favorable comment.
Embodiment
The present invention is further detailed explanation below by specific embodiment.
Embodiment 1
In the 250mL four-hole boiling flask that nitrogen protection, agitator, thermometer, fractional column device are housed; add 0.4mol water; 0.4mol technical grade dicyclopentadiene (85wt%); be heated to 80 ℃; splash into the 0.4mol MALEIC ANHYDRIDE in the 2h; temperature control is at 125 ℃ of hydrolysis reaction, and insulation is 190～230mgKOH/g until acid number under this temperature.Add 0.22mol ethylene glycol then, be warming up to 205 ℃ and carry out the polycondensation dehydration reaction, finish reaction after smaller or equal to 50mgKOH/g to the acid number of reactant, the reactant cooling is cooled to 180 ℃, the 200mg/kg Resorcinol that adds the resin total amount, pour the 30% vinylbenzene dilution back cooling discharge of resin total amount into, obtain the light unsaturated polyester resin of technical grade dicyclopentadiene preparation.
Embodiment 2
In the 250mL four-hole boiling flask that nitrogen protection, agitator, thermometer, fractional column device are housed; add 0.8mol water; 0.4mol technical grade dicyclopentadiene (78wt%); be heated to 120 ℃; splash into the 0.6mol MALEIC ANHYDRIDE in the 4h; temperature control is at 120 ℃ of hydrolysis reaction, and insulation is 220～260mgKOH/g until acid number under this temperature.Add the 0.22mol neopentyl glycol then, 0.22mol ethylene glycol, be warming up to 160 ℃ and carry out the polycondensation dehydration reaction, finish reaction after smaller or equal to 50mgKOH/g to the acid number of reactant, the reactant cooling is cooled to 140 ℃, the 200mg/kg Resorcinol that adds the resin total amount, 30% vinylbenzene of pouring the resin total amount into dilutes the back cooling discharge, obtains the light unsaturated polyester resin of technical grade dicyclopentadiene preparation.
Embodiment 3
In the 250mL four-hole boiling flask that nitrogen protection, agitator, thermometer, fractional column device are housed; add 0.4mol water; 0.2mol technical grade dicyclopentadiene (82wt%); be heated to 150 ℃; splash into the 0.4mol MALEIC ANHYDRIDE in the 4h; temperature control is at 150 ℃ of hydrolysis reaction, and insulation is 250～290mgKOH/g until acid number under this temperature.Add the 0.2mol m-phthalic acid then, 0.3mol neopentyl glycol, 0.3mol propylene glycol, be warming up to 185 ℃ and carry out the polycondensation dehydration reaction, finish reaction after smaller or equal to 50mgKOH/g to the acid number of reactant, the reactant cooling is cooled to 180 ℃, adds the 200mg/kg Resorcinol of resin total amount, pour the 30% vinylbenzene dilution back cooling discharge of resin total amount into, obtain the light unsaturated polyester resin of technical grade dicyclopentadiene preparation.
Embodiment 4
In the 250mL four-hole boiling flask that nitrogen protection, agitator, thermometer, fractional column device are housed; add 0.3mol water; 0.2mol technical grade dicyclopentadiene (85wt%); be heated to 90 ℃; splash into the 0.2mol MALEIC ANHYDRIDE in the 2h; temperature control is at 100 ℃ of hydrolysis reaction, and insulation is 190～230mgKOH/g until acid number under this temperature.Add the anti-butylene pentanedioic acid of 0.4mol then, 0.6mol propylene glycol, be warming up to 200 ℃ and carry out the polycondensation dehydration reaction, finish reaction after smaller or equal to 50mgKOH/g to the acid number of reactant, the reactant cooling is cooled to 110 ℃, the 200mg/kg Resorcinol that adds the resin total amount, 30% vinylbenzene of pouring the resin total amount into dilutes the back cooling discharge, obtains the light unsaturated polyester resin of technical grade dicyclopentadiene preparation.
Embodiment 5
In the 250mL four-hole boiling flask that nitrogen protection, agitator, thermometer, fractional column device are housed; add 0.3mol water; 0.2mol technical grade dicyclopentadiene (85wt%); be heated to 80 ℃; splash into the 0.2mol MALEIC ANHYDRIDE in the 2h; temperature control is at 130 ℃ of hydrolysis reaction, and insulation is 190～230mgKOH/g until acid number under this temperature.Add 0.4mol tetrahydrophthalic anhydride, 0.3mol glycol ether, 0.3mol dipropylene glycol then, be warming up to 200 ℃ and carry out the polycondensation dehydration reaction, finish reaction after smaller or equal to 50mgKOH/g to the acid number of reactant, the reactant cooling is cooled to 180 ℃, the 200mg/kg Resorcinol that adds the resin total amount, pour the 30% vinylbenzene dilution back cooling discharge of resin total amount into, obtain the light unsaturated polyester resin of technical grade dicyclopentadiene preparation.
The comparative example 1
In the 250mL four-hole boiling flask that nitrogen protection, agitator, thermometer, fractional column device are housed; add the 0.4mol MALEIC ANHYDRIDE; 0.4mol technical grade dicyclopentadiene (85wt%); be heated to 80 ℃ of fusions; splash into 0.4mol water in the 3h; temperature control is at 125 ℃ of hydrolysis maleic acids, and insulation is 190～230mgKOH/g until acid number under this temperature.Splash into 0.22mol ethylene glycol then, temperature control was 205 ℃ of polycondensation dehydration reactions 8 hours, acid number to reactant finishes reaction smaller or equal to 50mgKOH/g, the reactant cooling is cooled to 180 ℃, the 200mg/kg Resorcinol that adds the resin total amount, pour the vinylbenzene dilution back cooling discharge of resin 30% into, obtain technical grade dicyclopentadiene and prepare modified unsaturated polyester resin.
The comparative example 2
In the 500mL four-hole boiling flask that nitrogen protection, agitator, thermometer, fractional column device are housed, add 2.0mol MALEIC ANHYDRIDE and 1.6mol dicyclopentadiene, and add catalyst composition phosphoric acid and the toluene sulfonic acide (weight ratio 6: 1) of 0.81g.Stir and heat up, when temperature rises to more than 100 ℃, add 2mol water, control reaction temperature is 150～170 ℃, reacts 2 hours, adds 1.6mol propylene glycol and 0.16mol glycerol, heats up gradually, constantly fractionates out the water in the system.When the acid number of reactant is 90～100mgKOH/g, add stopper p-ten.-butylcatechol 200mg/kg, continue reaction, when temperature of reaction rises to 200～205 ℃, finish reaction after less than 50mgKOH/g to the acid number of reactant.The reactant cooling is cooled to 100～110 ℃, adds the 500mg/kg Resorcinol, adds the vinylbenzene dilution back cooling discharge of resin 30%, promptly gets dicyclic pentylene modified unsaturated polyester resin.It is light yellow that product is, transparent liquid.
Table 1: the physicochemical property of unsaturated polyester resin product among the embodiment
| Project | The resin outward appearance | Colourity (Gardner) | Acid number (mgKOH/g) | Solid content (%) | Gel time (min) | Viscosity (Pas) |
| Embodiment 1 | Light yellow transparent | 2 | 18 | 70.1 | 15.5 | 0.253 |
| Embodiment 2 | Light yellow transparent | 3 | 20 | 69.3 | 18.0 | 0.296 |
| Embodiment 3 | Light yellow transparent | 2 | 18 | 70.0 | 12.5 | 0.284 |
| Embodiment 4 | Light yellow transparent | 3 | 19 | 68.8 | 16.5 | 0.302 |
| Embodiment 5 | Light yellow transparent | 2 + | 20 | 69.2 | 16.0 | 0.355 |
| The comparative example 1 | Brown transparent | 7 + | 19 | 70.3 | 14.5 | 0.276 |
| The comparative example 2 | Light yellow transparent | 3 + | 21 | 69.0 | 12.0 | 0.352 |
Colourity is tested by GB/T22295-2008 color of transparent liquids measuring method (Gardner's colourity).The resin voltinism is tested by GB GB/T 7193-2008 unsaturated polyester resin test method.
Table 2: embodiment 1 and comparative example's 1 molecular resin amount GPC test comparison
| Project | Embodiment 1 | The comparative example 1 |
| Mn | 550 | 558 |
| Mw | 2241 | 2487 |
| Mw/Mn | 4.076 | 4.459 |
Table 3: embodiment 1 and the contrast of comparative example's 1 casting matrix physical and mechanical property
| Title | Unit | Embodiment 1 | The comparative example 1 |
| Tensile strength | MPa | 47.6 | 46.9 |
| Modulus in tension | MPa×10 3 | 3.8 | 3.7 |
| Tension set | ％ | 1.4 | 1.4 |
| Flexural strength | MPa | 75 | 71.8 |
| Bending elastic modulus | MPa×10 3 | 3.7 | 3.8 |
| Heat-drawn wire | ℃ | 94.1 | 98.4 |
| Ba Keer hardness | Barcol | 45 | 46 |
The testing method of pour mass: GB/T 2567-2008 casting resin method for testing performance.
Contrasted as can be known by table 1, table 2, table 3 data: existing preparation method compares with original preparation method, and not only appearance color shoals, and the dicyclic pentylene modified unsaturated polyester resin of existing simultaneously method preparation and the performance of original preparation do not reduce.
Claims (6)
1. the method for a preparing unsaturated polyster resin by industrial dicyclopentadiene is characterized in that this method carries out as follows:
A, in the four-hole container that nitrogen protection, agitator, thermometer, fractional column device are housed, add mol ratio and be 1: 1～1: 2 technical grade dicyclopentadiene and water, be warming up to 80～150 ℃, drip unsaturated dicarboxylic acid anhydride; Dropwise the back in 100～150 ℃ of insulations, continue to react to acid number be 190～290mgKOH/g;
B, the mixture that continues to add dibasic alcohol in the four-hole container or add dibasic alcohol and diprotic acid or acid anhydrides are warming up to 160～205 ℃, carry out the polycondensation dehydration reaction, to acid number be smaller or equal to 50mgKOH/g;
C, reactant is cooled to 110～180 ℃, after add-on is the 200mg/kg Resorcinol stopper of resin total amount, pouring volume is the 30% vinylbenzene cross-linking monomer dilution of resin total amount, promptly gets the light unsaturated polyester resin of technical grade dicyclopentadiene preparation after mixing.
2. the method for preparing unsaturated polyster resin by industrial dicyclopentadiene according to claim 1, the purity that it is characterized in that described dicyclopentadiene is 78～85wt%.
3. the method for preparing unsaturated polyster resin by industrial dicyclopentadiene according to claim 1, it is characterized in that the unsaturated dicarboxylic acid anhydride described in the step a is: MALEIC ANHYDRIDE, MALEIC ANHYDRIDE and technical grade dicyclopentadiene mol ratio are 2: 1～1: 1.
4. the method for preparing unsaturated polyster resin by industrial dicyclopentadiene according to claim 1, it is characterized in that the dibasic alcohol described in the step b is ethylene glycol, propylene glycol, neopentyl glycol, glycol ether, dipropylene glycol, propoxylated bisphenol, 1,4-butyleneglycol, 2, the 3-butyleneglycol.
5. the method for preparing unsaturated polyster resin by industrial dicyclopentadiene according to claim 1 is characterized in that diprotic acid described in the step b or acid anhydrides are: Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, hexanodioic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, tetrahydrophthalic anhydride, Succinic Acid, pentanedioic acid, pimelic acid, the special acid in sea, PHT4, tetrachlorophthalic anhydride.
6. the method for preparing unsaturated polyster resin by industrial dicyclopentadiene according to claim 1, the colourity that it is characterized in that described unsaturated polyester resin is tested by GB/T22295-2008 color of transparent liquids measuring method, and its colourity is smaller or equal to No. 3, Gardner color scale.
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| CN103193966B (en) * | 2013-04-27 | 2015-04-01 | 肇庆福田化学工业有限公司 | Unsaturated polyester resin for artificial stone and synthesis method thereof |
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