CN103030745A - Water-based photo-cured unsaturated polyester and preparation method thereof - Google Patents
Water-based photo-cured unsaturated polyester and preparation method thereof Download PDFInfo
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- CN103030745A CN103030745A CN2012105237692A CN201210523769A CN103030745A CN 103030745 A CN103030745 A CN 103030745A CN 2012105237692 A CN2012105237692 A CN 2012105237692A CN 201210523769 A CN201210523769 A CN 201210523769A CN 103030745 A CN103030745 A CN 103030745A
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Abstract
The invention relates to water-based photo-cured unsaturated polyester with an ultraviolet curing characteristic and a synthetic method thereof. The water-based photo-cured unsaturated polyester is characterized by having the following chemical structural formula shown in the specification. The polyester prepared by the method has the characteristics of high stability, high water resistance, high curing speed and high glossiness.
Description
Technical field
The present invention relates to water-based unsaturated polyester and synthetic method thereof that a class has the ultraviolet light polymerization characteristic.
Background technology
Germany Bayer company has developed first-generation ultraviolet-curing paint (UVCC) afterwards from the 6O age in 20th century, because this technology meets the 3E principle fully, but have the characteristics such as curing speed is fast, non-volatility solvent, save energy, the low automatic production of expense, keeping fast development always.Because the used main component of photo-cured coating system is that oligopolymer generally has higher viscosity, must add before use more reactive thinner with the adjusting viscosity, improve rheological, and these reactive thinner major parts have toxicity and pungency; On the other hand, along with improving gradually and various countries' environmental regulation increasingly strict of people's environmental consciousness, water-borne coatings has become one of main direction of paint development, and its low-viscosity of very easily regulating makes it to be suitable for to spray.In this case, the UV solidified aqueous coating arises at the historic moment, and it combines both advantages, becomes very active at present research and development field.Unsaturated polyester resin (UPR) has good mechanical property, electrical property and resistance to chemical corrosion, and complete processing is easy, so the Abroad in Recent Years development is comparatively rapid, is to develop faster one of kind in the thermosetting resin.Be widely used in the fields such as industry, agricultural, traffic and transportation.Therefore, the study on the synthesis of photocuring water-based unsaturated polyester is that the development of society and market economy is required, has higher using value.
The O of ground state
2Be diradical in essence, therefore have stronger addition active to the living radical that produces in the light-initiated process, form more stable peroxylradicals.This process rate is very fast, can compete mutually the addition reaction of monomer with living radical, and is the most aobvious to the inhibition of polymerization process.Oxygen inhibition is very large to the harm of UV solidification process, especially when coating thickness is thinner.The oxygen molecule that not only dissolves in the formula system hinders polymerization, and in light-initiated process, along with the consumption of oxygen molecule in the curing system, the airborne oxygen of coatingsurface also can diffuse to rapidly in the solidified coating, continues to hinder polymerization.The oxygen that constantly diffuses to coating inside from the external world is the major cause that hinders polymerization.Oxygen inhibition is the easiest shallow top layer that occurs in coating or whole than in the shallow layer also, because in these zones, the oxygen molecule diffusion in the environment is easier.
During photocuring, the oxygen inhibition effect usually causes the coating bottom to solidify, the surface is uncured and the situation of stickness in air.Oxygen inhibition finally can cause the coating top layer oxidisability structures such as great amount of hydroxy group, carbonyl, peroxy to occur, thereby affects the permanent stability of coating, even may affect the performances such as hardness, glossiness and resistance to marring of solidifying rear paint film.
Summary of the invention
The purpose of this invention is to provide a kind of aqueous photo-curing unsaturated polyester and preparation method thereof, the polyester of the method preparation has the characteristics of good stability.
To achieve these goals, the technical solution used in the present invention is: the aqueous photo-curing unsaturated polyester is characterized in that its chemical structural formula is:
In the formula (1): R
1Be H or CH
3R
2Be H or CH
3R
3For
R
4For
Or
P wherein
1=2,3,4,5,6,7,8,9 or 10, p
2=1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20, p
3=1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24 or 25;
q
1Be 1 or 2; q
2Be 1 or 2; M=2,3,4,5 or 6, n=0,1,2,3,4,5,6,7 or 8.
Press such scheme, q1+q2=p, p=2 or 3.
The preparation method of above-mentioned aqueous photo-curing unsaturated polyester (adopting one of method of mass polymerization), it is characterized in that: it may further comprise the steps: 1) under the protection of nitrogen, be the polyol blends of 40-60 with mass parts, the polyprotonic acid mixture of 40-60 mass parts, 0.1-0.3 the oxidation inhibitor of mass parts joins with in the four-hole reactor that stirs, and adopts mass polymerization;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. three kinds of raw materials compositions of dimethylol propionic acid, wherein the TriMethylolPropane(TMP) mono allyl ether to account for the 33%-82.5%(mass parts of polyol blends quality be 20-33), the 16.6-45%(mass parts of the shared polyol blends quality of dimethylol propionic acid is 10-18);
Described polyprotonic acid mixture is comprised of following two kinds of raw materials: 1. a kind of or two kinds of mixing by any proportioning in monounsaturated dicarboxylic acid or saturated (comprise contain phenyl ring) acid anhydrides, 2. and unsaturated dibasic acid or contain the carbon-carbon double bond unsaturated acid anhydride of (not comprising phenyl ring); Wherein, unsaturated dibasic acid or the 16.6-52.5%(mass parts that contains the shared polyprotonic acid mixture quality of unsaturated acid anhydride of carbon-carbon double bond (not comprising phenyl ring) are 10-21);
2) be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, keeps refluxing not draining under this state of insulation 1h(); Then be warming up to 180 ℃ with 1h, and be incubated 2h(and keeping reaction under this temperature) after, under vacuum tightness 0.040MPa, keep again the 0.5-1h dehydration; Increasing nitrogen amount that can be suitable is beneficial to draining, reacts the theoretical value (this theoretical value has the different theories value according to formulating of recipe) that reaches formulating of recipe to acid number;
3) be cooled to 150 ℃, and add the stopper of 0.2-0.5 mass parts, continue to be cooled to 95 ℃; The glycidyl methacrylate that drips the 7-15 mass parts adds in the reactor, and adds 0.1-0.3 mass parts Tetramethylammonium iodide; React the theoretical value (this theoretical value has the different theories value according to formulating of recipe) that reaches formulating of recipe to acid number under this temperature; Be cooled to 65 ℃, the pH value that the adding neutralizing agent is neutralized to product is 7-8, obtains product (being unsaturated polyester); Product stirs and adds entry and dilutes (high-speed stirring 15min-30min, the rotating speed of described high-speed stirring is 800-1200 rev/min), the add-on of water is the 50%-200% of product (being equivalent to whole unsaturated polyester) quality, namely obtains the aqueous photo-curing unsaturated polyester.
The preparation method of above-mentioned aqueous photo-curing unsaturated polyester (adopt mass polymerization method two), it is characterized in that: it may further comprise the steps: 1. under the protection of nitrogen, be the polyol blends of 40-60 with mass parts, the polyprotonic acid mixture of 35-55 mass parts, 0.1-0.3 the oxidation inhibitor of mass parts joins with in the four-hole reactor that stirs, and adopts mass polymerization;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. three kinds of raw materials compositions of dimethylol propionic acid, wherein the TriMethylolPropane(TMP) mono allyl ether to account for the 33%-82.5%(mass parts of polyol blends quality be 20-33), the 16.6-45%(mass parts of the shared polyol blends quality of dimethylol propionic acid is 10-18);
Described polyprotonic acid mixture is comprised of following two kinds of raw materials: 1. a kind of or two kinds of mixing by any proportioning in monounsaturated dicarboxylic acid or saturated (comprise contain phenyl ring) acid anhydrides, 2. and unsaturated dibasic acid or contain the carbon-carbon double bond unsaturated acid anhydride of (not comprising phenyl ring); Wherein, unsaturated dibasic acid or the 8.5%-27.5%(mass parts that contains the shared polyprotonic acid mixture quality of unsaturated acid anhydride of carbon-carbon double bond (not comprising phenyl ring) are 5-11);
2. be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, keeps refluxing not draining under this state of insulation 1h(); Then be warming up to 180 ℃ with 1h, add again the unsaturated acid of 5-10 mass parts or contain the carbon-carbon double bond unsaturated acid anhydride of (not comprising phenyl ring), and be incubated 2h(and keeping reaction under this temperature) after, under vacuum tightness 0.040MPa, keep again the 0.5-1h dehydration; Increasing nitrogen amount that can be suitable is beneficial to draining, reacts the theoretical value (this theoretical value has the different theories value according to formulating of recipe) that reaches formulating of recipe to acid number;
3. be cooled to 150 ℃, and add the stopper of 0.2-0.5 mass parts, continue to be cooled to 95 ℃; The glycidyl methacrylate that drips the 7-15 mass parts enters in the reactor, and adds 0.1-0.3 mass parts Tetramethylammonium iodide, reacts the theoretical value (this theoretical value has the different theories value according to formulating of recipe) that reaches formulating of recipe to acid number under this temperature; Be cooled to 65 ℃, the pH value that the adding neutralizing agent is neutralized to product is 7-8, obtains product (being unsaturated polyester); Product stirs and adds entry and dilutes (high-speed stirring 15min-30min, the rotating speed of described high-speed stirring is 800-1200 rev/min), the add-on of water is the 50%-200% of product (being equivalent to whole unsaturated polyester) quality, namely obtains the aqueous photo-curing unsaturated polyester.
Press such scheme, polyvalent alcohol is propylene glycol, ethylene glycol, hexylene glycol, glycol ether, dipropylene glycol or neopentyl glycol etc.
Press such scheme, described monounsaturated dicarboxylic acid is that any one or any two or more in hexanodioic acid, suberic acid, Succinic Acid, propanedioic acid, the pentanedioic acid etc. is by the mixing of any proportioning; Described saturated (comprise contain phenyl ring), acid anhydrides was Tetra hydro Phthalic anhydride, Succinic anhydried, trimellitic acid 1,2-anhydride etc.; Unsaturated dibasic acid is toxilic acid or fumaric acid etc.; The unsaturated acid anhydride that contains carbon-carbon double bond (not comprising phenyl ring) is maleic anhydride.
Press such scheme, described oxidation inhibitor is triphenyl phosphite.
Press such scheme, described stopper is selected Resorcinol, methyl hydroquinone, para benzoquinone, tertiary butyl catechol, 2, and any one or any two or more in 6-di-tert-butyl-4-cresols etc. is by the mixing of any proportioning.
Press such scheme, described neutralizing agent is organic amine neutralizing agent (N, N--dimethylethanolamine).
End-use: aqueous photo-curing unsaturated polyester of the present invention can be used for woodwork coating, at woodenware and wood finishing field higher using value is arranged.Because aqueous photo-curing unsaturated polyester of the present invention (resin) dilute with water has avoided solvent and reactive thinner to the injury of human body contact, has realized low VOC, be easy to simultaneously the recovery reprocessing of paper, and can be applied to gloss oil for paper.The present invention also can be used for the field that other can not the high temperature film forming, such as: Electronic Packaging, tackiness agent, printing board material, electronic industry etc.
The invention has the beneficial effects as follows: the polyester of the method preparation has good stability, water-fast good, curing speed is fast, glossiness is high characteristics.
Embodiment
Further illustrate by the following examples content of the present invention, but content of the present invention not only is confined to the following examples.Embodiment 1(adopts one of method of mass polymerization):
The preparation method of aqueous photo-curing unsaturated polyester (one of mass polymerization), it may further comprise the steps:
1. under the protection of nitrogen; with 33.00g TriMethylolPropane(TMP) mono allyl ether; 9.23g neopentyl glycol (being polyvalent alcohol); 17.53g dimethylol propionic acid; 14.77g Tetra hydro Phthalic anhydride (being saturated (comprise and contain phenyl ring) acid anhydrides); 10.15g maleic anhydride [for containing the carbon-carbon double bond unsaturated acid anhydride of (not comprising phenyl ring)]; 15.84g hexanodioic acid (being monounsaturated dicarboxylic acid); and 0.26g oxidation inhibitor (triphenyl phosphite) joins in the four-hole reactor with agitator, prolong, thermometer and dropper, adopts mass polymerization.
2. be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, keeps refluxing not draining under this state of insulation 1h().Then be warming up to 180 ℃ with 1h, and insulation 2h, and under this temperature, keep reaction, under vacuum tightness 0.040MPa, keep again the 0.5-1h dehydration.Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches 80.
3. be cooled to 150 ℃, and add the 0.30g stopper, continue to be cooled to 95 ℃.Drip 14.5g glycidyl methacrylate (GMA) and enter in the reactor, and add the 0.30g Tetramethylammonium iodide, drip off half an hour.React to acid number to 20 under this temperature.Be cooled to 65 ℃, and add 3g neutralizing agent neutralize (the pH value to product is 7-8), obtain product (being unsaturated polyester), the quality of product is 110g, stir 15min under the speed of 800r/min, then slowly add 140g water dilution (high-speed stirring half an hour), namely obtain aqueous photo-curing unsaturated polyester (the aqueous photo-curing unsaturated polyester of terminal hydroxy group).
The used oxidation inhibitor of this experiment is triphenyl phosphite.
The used stopper of this experiment is Resorcinol.
The used neutralizing agent of this experiment is N, the N-dimethylethanolamine.
The method test of pencil hardometer is adopted in the hardness test of this experiment, and test result sees the following form.
The water-fast test of this experiment is to carry out in 25 ℃ of water, and is non-foaming with film, nondiscoloration, and not coming off is criterion of acceptability, test result sees the following form.
Storage stability is placed in the vial at normal temperatures, and is not stratified with resin solution, and nondiscoloration is criterion of acceptability.Test result sees the following form.
The technical target of the product of embodiment 1 is as shown in table 1 below:
Table 1
| Outward appearance | Little Huang, transparent (glossiness is high) |
| Solid content | The 43.1wt%(height contains admittedly) |
| PH value (after the dilution) | 8 |
| Acid number (solid part) | 20 |
| Number-average molecular weight | 900 |
| Hardness | 1h |
| Water-fast (25 ℃) | 72h is unchanged |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 1 explanation: the polyester of the method preparation has that good stability, height contain admittedly, curing speed fast (2500w high voltage mercury lamp 20s fast filming), characteristics that glossiness is high.
Embodiment 2(adopt mass polymerization method two):
The preparation method of aqueous photo-curing unsaturated polyester (adopt mass polymerization method two), it may further comprise the steps:
1. under the protection of nitrogen; with 20.00g TriMethylolPropane(TMP) mono allyl ether; 16.50g neopentyl glycol; 12.00g dimethylol propionic acid; 11.00g Tetra hydro Phthalic anhydride, 9.00g maleic anhydride, 10.00g hexanodioic acid; and 0.21g oxidation inhibitor joins in the four-hole reactor with agitator, prolong, thermometer and dropper, adopts mass polymerization.
2. be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, keeps refluxing not draining under this state of insulation 1h().Then be warming up to 180 ℃ with 1h, add again the 9.00g maleic anhydride, and insulation 2h, and after keeping reaction under this temperature, under vacuum tightness 0.040MPa, keep again 0.5 dehydration.Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches 62.
3. be cooled to 150 ℃, and add the 0.32g stopper, continue to be cooled to 95 ℃.Drip 8.00g glycidyl methacrylate (GMA) and enter in the reactor, and add 0.22g Tetramethylammonium iodide (catalyzer).React to acid number to 22 under this temperature.Be cooled to 65 ℃, and add 2.40g neutralizing agent neutralize (the pH value to product is 7-8), obtain product (being unsaturated polyester), the quality of product is 90g, stir 15min under the speed of 800r/min, then slowly add 180g water dilution (high-speed stirring half an hour), namely obtain aqueous photo-curing unsaturated polyester (the aqueous photo-curing unsaturated polyester of terminal hydroxy group).
The used oxidation inhibitor of this experiment is triphenyl phosphite.
The used stopper of this experiment is Resorcinol.
The used neutralizing agent of this experiment is N, the N-dimethylethanolamine.
The method test of pencil hardometer is adopted in the hardness test of this experiment, and test result sees the following form.
The water-fast test of this experiment is to carry out in 25 ℃ of water, and is non-foaming with film, nondiscoloration, and not coming off is criterion of acceptability, test result sees the following form.
Storage stability is placed in the vial at normal temperatures, and is not stratified with resin solution, and nondiscoloration is criterion of acceptability.Test result sees the following form.
The technical target of the product of embodiment 2 is as shown in table 2 below:
Table 2
| Outward appearance | Little Huang, transparent |
| Solid content | 33.3% |
| PH value (after the dilution) | 8 |
| Acid number (solid part) | 22 |
| Number-average molecular weight | 2300 |
| Hardness | 3h(hardness is high) |
| Water-fast (25 ℃) | 120h unchanged (water-fast good) |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 2 explanation: the polyester of the method preparation has hardness height, good stability, water-fast good, curing speed fast (2500w high voltage mercury lamp 20s fast filming), characteristics that glossiness is high.
Embodiment 3(adopts one of method of mass polymerization):
The preparation method of aqueous photo-curing unsaturated polyester (adopting one of method of mass polymerization), it may further comprise the steps:
1. under the protection of nitrogen; with 15.00g TriMethylolPropane(TMP) mono allyl ether; 18.75g neopentyl glycol; 10.00g dimethylol propionic acid; 25.00g Tetra hydro Phthalic anhydride, 11.88g maleic anhydride, 18.75g hexanodioic acid; and 0.26g oxidation inhibitor joins in the four-hole reactor with agitator, prolong, thermometer and dropper, adopts mass polymerization.
2. be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, keeps refluxing not draining under this state of insulation 1h().Then be warming up to 180 ℃ with 1h, and insulation 2h, and after keeping reaction under this temperature, under vacuum tightness 0.040MPa, keep again the 0.5-1h dehydration.Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches 150.
3. be cooled to 150 ℃, and add the 0.30g stopper, continue to be cooled to 95 ℃.Drip 14g glycidyl methacrylate (GMA) and enter in the reactor, and add the 0.30g Tetramethylammonium iodide, drip off half an hour.React to acid number to 80 under this temperature.Be cooled to 65 ℃, and adding 10gN, N-dimethylethanolamine neutralizing agent neutralize (being 7-8 to the pH value of product), obtain product (being unsaturated polyester), the quality of product is 101g, stir 15min under the speed of 800r/min, then slowly add 135g water dilution (high-speed stirring half an hour), namely obtain the aqueous photo-curing unsaturated polyester.
The used oxidation inhibitor of this experiment is triphenyl phosphite.
The used stopper of this experiment is Resorcinol.
The used neutralizing agent of this experiment is N, the N-dimethylethanolamine.
The method test of pencil hardometer is adopted in the hardness test of this experiment, and test result sees the following form.
The water-fast test of this experiment is to carry out in 25 ℃ of water, and is non-foaming with film, nondiscoloration, and not coming off is criterion of acceptability, test result sees the following form.
Storage stability is placed in the vial at normal temperatures, and is not stratified with resin solution, and nondiscoloration is criterion of acceptability.Test result sees the following form.
The technical target of the product of embodiment 3 is as shown in table 3 below:
Table 3
| Outward appearance | Little Huang, transparent |
| Solid content | 40% |
| PH value (after the dilution) | 8 |
| Acid number (solid part) | 80 |
| Number-average molecular weight | 1300 |
| Hardness | 2h |
| Water-fast | It is good that 96h(is water-fast) |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 3 explanation: the polyester of the method preparation has good stability, admittedly contains higher, water-fast good, curing speed fast (2500w high voltage mercury lamp 20s fast filming), characteristics that glossiness is high.
Embodiment 4
Substantially the same manner as Example 1, difference is: " neopentyl glycol " replaced by " propylene glycol "; " hexanodioic acid " replaced by " suberic acid "; " Resorcinol " replaced by " methyl hydroquinone ".Technical target of the product is identical with embodiment 1.
Embodiment 5
Substantially the same manner as Example 1, difference is: " neopentyl glycol " replaced by " ethylene glycol "; " hexanodioic acid " replaced by " Succinic Acid "; " Resorcinol " replaced by " para benzoquinone ".Technical target of the product is identical with embodiment 1.
Embodiment 6
Substantially the same manner as Example 1, difference is: " neopentyl glycol " replaced by " hexylene glycol "; " hexanodioic acid " replaced by " propanedioic acid "; " Resorcinol " replaced by " tertiary butyl catechol ".Technical target of the product is identical with embodiment 1.
Embodiment 7
Substantially the same manner as Example 1, difference is: " neopentyl glycol " replaced by " glycol ether "; " hexanodioic acid " replaced by " pentanedioic acid "; " Resorcinol " replaced by " 2,6-di-tert-butyl-4-cresols ".Technical target of the product is identical with embodiment 1.
Embodiment 8
Substantially the same manner as Example 1, difference is: " neopentyl glycol " replaced by " dipropylene glycol "; " Resorcinol " replaced by " methyl hydroquinone and para benzoquinone ", methyl hydroquinone 0.22g, para benzoquinone 0.12g.Technical target of the product is identical with embodiment 1.
Embodiment 9
The preparation method of aqueous photo-curing unsaturated polyester (adopting one of method of mass polymerization), it may further comprise the steps: 1) under the protection of nitrogen, polyol blends with 60g, the polyprotonic acid mixture of 60g, 0.3g oxidation inhibitor join with in the four-hole reactor that stirs, adopt mass polymerization;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. three kinds of raw materials compositions of dimethylol propionic acid, wherein the TriMethylolPropane(TMP) mono allyl ether accounts for 82.5% of polyol blends quality, 16.6% of the shared polyol blends quality of dimethylol propionic acid;
Described polyprotonic acid mixture is comprised of following two kinds of raw materials: 1. saturated (comprise contain phenyl ring) acid anhydrides, 2. and contain the carbon-carbon double bond unsaturated acid anhydride of (not comprising phenyl ring); Wherein, contain carbon-carbon double bond (not comprising phenyl ring) the shared polyprotonic acid mixture quality of unsaturated acid anhydride 52.5%;
Described polyvalent alcohol is propylene glycol.Saturated (comprise contain phenyl ring), acid anhydrides was Tetra hydro Phthalic anhydride.The unsaturated acid anhydride that contains carbon-carbon double bond (not comprising phenyl ring) is maleic anhydride.Described oxidation inhibitor is triphenyl phosphite.
2) be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, keeps refluxing not draining under this state of insulation 1h(); Then be warming up to 180 ℃ with 1h, and be incubated 2h(and keeping reaction under this temperature) after, under vacuum tightness 0.040MPa, keep again the 0.5-1h dehydration; Increasing nitrogen amount that can be suitable is beneficial to draining, reacts the theoretical value 168 that reaches formulating of recipe to acid number;
3) be cooled to 150 ℃, and add the stopper of 0.5g, continue to be cooled to 95 ℃; The glycidyl methacrylate that drips 15g adds in the reactor, and adds the 0.3g Tetramethylammonium iodide; React the theoretical value 100 that reaches formulating of recipe to acid number under this temperature; Be cooled to 65 ℃, the pH value that adding 12g neutralizing agent is neutralized to product is 7-8, obtains product (being unsaturated polyester); Product stirs and adds entry dilution (high-speed stirring 15min-30min, the rotating speed of described high-speed stirring are 800-1200 rev/min), and the add-on of water is 100% of product (being equivalent to whole unsaturated polyester) quality, namely obtains the aqueous photo-curing unsaturated polyester.
Described stopper is selected Resorcinol.Described neutralizing agent is organic amine neutralizing agent (N, N-dimethylethanolamine).
The method test of pencil hardometer is adopted in the hardness test of this experiment, and test result sees the following form.
The water-fast test of this experiment is to carry out in 25 ℃ of water, and is non-foaming with film, nondiscoloration, and not coming off is criterion of acceptability, test result sees the following form.
Storage stability is placed in the vial at normal temperatures, and is not stratified with resin solution, and nondiscoloration is criterion of acceptability.Test result sees the following form.
The technical target of the product of embodiment 9 is as shown in table 4 below:
Table 4
| Outward appearance | Little Huang, transparent (glossiness is high) |
| Solid content | 50wt% |
| PH value (after the dilution) | 8 |
| Acid number (solid part) | 100 |
| Number-average molecular weight | 900 |
| Hardness | 1h |
| Water-fast (25 ℃) | 48h is unchanged |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 4 explanation: the polyester of the method preparation has that good stability, height contain admittedly, curing speed fast (2500w high voltage mercury lamp 20s fast filming), characteristics that glossiness is high.
Embodiment 10
The preparation method of aqueous photo-curing unsaturated polyester (adopting one of method of mass polymerization), it may further comprise the steps: 1) under the protection of nitrogen, polyol blends with 40g, the polyprotonic acid mixture of 40g, 0.1g oxidation inhibitor join with in the four-hole reactor that stirs, adopt mass polymerization;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. three kinds of raw materials compositions of dimethylol propionic acid, wherein the TriMethylolPropane(TMP) mono allyl ether accounts for 33% of polyol blends quality, 45% of the shared polyol blends quality of dimethylol propionic acid;
Described polyprotonic acid mixture is comprised of following two kinds of raw materials: 1. monounsaturated dicarboxylic acid, 2. and unsaturated dibasic acid; Wherein, 52.5% of the shared polyprotonic acid mixture quality of unsaturated dibasic acid;
Described polyvalent alcohol is propylene glycol.Described monounsaturated dicarboxylic acid is hexanodioic acid; Unsaturated dibasic acid is fumaric acid.Described oxidation inhibitor is triphenyl phosphite.
2) be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, keeps refluxing not draining under this state of insulation 1h(); Then be warming up to 180 ℃ with 1h, and be incubated 2h(and keeping reaction under this temperature) after, under vacuum tightness 0.040MPa, keep again the 0.5-1h dehydration; Increasing nitrogen amount that can be suitable is beneficial to draining, reacts the theoretical value 105 that reaches formulating of recipe to acid number;
3) be cooled to 150 ℃, and add the stopper of 0.2g, continue to be cooled to 95 ℃; The glycidyl methacrylate that drips 7g adds in the reactor, and adds the 0.1g Tetramethylammonium iodide; React the theoretical value 70 that reaches formulating of recipe to acid number under this temperature; Be cooled to 65 ℃, the pH value that the adding neutralizing agent is neutralized to product is 7-8, obtains product (being unsaturated polyester); Product stirs and adds entry dilution (high-speed stirring 15min-30min, the rotating speed of described high-speed stirring are 800-1200 rev/min), and the add-on of water is 200% of product (being equivalent to whole unsaturated polyester) quality, namely obtains the aqueous photo-curing unsaturated polyester.
Described stopper is selected Resorcinol.Described neutralizing agent is organic amine neutralizing agent (N, N-dimethylethanolamine).
The method test of pencil hardometer is adopted in the hardness test of this experiment, and test result sees the following form.
The water-fast test of this experiment is to carry out in 25 ℃ of water, and is non-foaming with film, nondiscoloration, and not coming off is criterion of acceptability, test result sees the following form.
Storage stability is placed in the vial at normal temperatures, and is not stratified with resin solution, and nondiscoloration is criterion of acceptability.Test result sees the following form.
The technical target of the product of embodiment 10 is as shown in table 5 below:
Table 5
| Outward appearance | Little Huang, transparent (glossiness is high) |
| Solid content | 33wt% |
| PH value (after the dilution) | 8 |
| Acid number (solid part) | 70 |
| Number-average molecular weight | 2800 |
| Hardness | 3h(hardness is high) |
| Water-fast (25 ℃) | 120h unchanged (water-fast good) |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 5 explanation: the polyester of the method preparation has that good stability, hardness are high, curing speed fast (2500w high voltage mercury lamp 20s fast filming), characteristics that glossiness is high.
Embodiment 12
Substantially the same manner as Example 1, difference is: " Tetra hydro Phthalic anhydride " replaced by " Succinic anhydried ".Technical target of the product is identical with embodiment 1.
Embodiment 13
Substantially the same manner as Example 1, difference is: " Tetra hydro Phthalic anhydride " replaced by " trimellitic acid 1,2-anhydride ".Technical target of the product is identical with embodiment 1.
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (such as temperature, time etc.), interval value can both realize the present invention, do not enumerate one by one embodiment at this.
Claims (9)
1. aqueous photo-curing unsaturated polyester is characterized in that its chemical structural formula is:
In the formula (1): R
1Be H or CH
3R
2Be H or CH
3R
3For
R
4For
Or
P wherein
1=2,3,4,5,6,7,8,9 or 10, p
2=1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20, p
3=1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24 or 25;
q
1Be 1 or 2; q
2Be 1 or 2; M=2,3,4,5 or 6, n=0,1,2,3,4,5,6,7 or 8.
2. aqueous photo-curing unsaturated polyester according to claim 1 is characterized in that: q1+q2=p, p=2 or 3.
3. the preparation method of aqueous photo-curing unsaturated polyester as claimed in claim 1, it is characterized in that: it may further comprise the steps: 1) under the protection of nitrogen, be the polyol blends of 40-60 with mass parts, the polyprotonic acid mixture of 40-60 mass parts, the oxidation inhibitor of 0.1-0.3 mass parts join with in the four-hole reactor that stirs;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. three kinds of raw materials compositions of dimethylol propionic acid, wherein the TriMethylolPropane(TMP) mono allyl ether accounts for the 33%-82.5% of polyol blends quality, the 16.6-45% of the shared polyol blends quality of dimethylol propionic acid;
Described polyprotonic acid mixture is comprised of following two kinds of raw materials: 1. a kind of in monounsaturated dicarboxylic acid or the saturated acid anhydrides or two kinds of mixing by any proportioning, 2. and unsaturated dibasic acid or unsaturated acid anhydride; Wherein, the 16.6-52.5% of the shared polyprotonic acid mixture quality of unsaturated dibasic acid or unsaturated acid anhydride;
2) be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, insulation 1h; Then be warming up to 180 ℃ with 1h, and behind the insulation 2h, under vacuum tightness 0.040MPa, keep again the 0.5-1h dehydration;
3) be cooled to 150 ℃, and add the stopper of 0.2-0.5 mass parts, continue to be cooled to 95 ℃; The glycidyl methacrylate that drips the 7-15 mass parts adds in the reactor, and adds 0.1-0.3 mass parts Tetramethylammonium iodide; Be cooled to 65 ℃, the pH value that the adding neutralizing agent is neutralized to product is 7-8, obtains product; Product stirs and adds the entry dilution, and the add-on of water is the 50%-200% of product quality, namely obtains the aqueous photo-curing unsaturated polyester.
4. the preparation method of aqueous photo-curing unsaturated polyester as claimed in claim 1, it is characterized in that: it may further comprise the steps: 1. under the protection of nitrogen, be the polyol blends of 40-60 with mass parts, the polyprotonic acid mixture of 35-55 mass parts, the oxidation inhibitor of 0.1-0.3 mass parts join with in the four-hole reactor that stirs;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. three kinds of raw materials compositions of dimethylol propionic acid, wherein the TriMethylolPropane(TMP) mono allyl ether accounts for the 33%-82.5% of polyol blends quality, the 16.6-45% of the shared polyol blends quality of dimethylol propionic acid;
Described polyprotonic acid mixture is comprised of following two kinds of raw materials: 1. a kind of in monounsaturated dicarboxylic acid or the saturated acid anhydrides or two kinds of mixing by any proportioning, 2. and unsaturated dibasic acid or unsaturated acid anhydride; Wherein, the 8.5%-27.5% of the shared polyprotonic acid mixture quality of unsaturated dibasic acid or unsaturated acid anhydride;
2. be warming up to 140 ℃, insulation 1h is warming up to 150 ℃ again, insulation 1h; Then be warming up to 180 ℃ with 1h, add again unsaturated acid or the unsaturated acid anhydride of 5-10 mass parts, and behind the insulation 2h, under vacuum tightness 0.040MPa, keep again the 0.5-1h dehydration;
3. be cooled to 150 ℃, and add the stopper of 0.2-0.5 mass parts, continue to be cooled to 95 ℃; The glycidyl methacrylate that drips the 7-15 mass parts enters in the reactor, and adds 0.1-0.3 mass parts Tetramethylammonium iodide; Be cooled to 65 ℃, the pH value that the adding neutralizing agent is neutralized to product is 7-8, obtains product; Product stirs and adds the entry dilution, and the add-on of water is the 50%-200% of product quality, namely obtains the aqueous photo-curing unsaturated polyester.
5. according to the preparation method of the described aqueous photo-curing unsaturated polyester of claim 3-4, it is characterized in that: polyvalent alcohol is propylene glycol, ethylene glycol, hexylene glycol, glycol ether, dipropylene glycol or neopentyl glycol.
6. according to the preparation method of the described aqueous photo-curing unsaturated polyester of claim 3-4, it is characterized in that: described monounsaturated dicarboxylic acid is that any one or any two or more in hexanodioic acid, suberic acid, Succinic Acid, propanedioic acid, the pentanedioic acid is by the mixing of any proportioning; Described saturated acid anhydrides is Tetra hydro Phthalic anhydride, Succinic anhydried or trimellitic acid 1,2-anhydride; Unsaturated dibasic acid is toxilic acid or fumaric acid; Unsaturated acid anhydride is maleic anhydride.
7. according to the preparation method of the described aqueous photo-curing unsaturated polyester of claim 3-4, it is characterized in that: described oxidation inhibitor is triphenyl phosphite.
8. according to the preparation method of the described aqueous photo-curing unsaturated polyester of claim 3-4, it is characterized in that: described stopper is selected Resorcinol, methyl hydroquinone, para benzoquinone, tertiary butyl catechol, 2, and any one or any two or more in 6-di-tert-butyl-4-cresols is by the mixing of any proportioning.
9. according to the preparation method of the described aqueous photo-curing unsaturated polyester of claim 3-4, it is characterized in that: described neutralizing agent is the organic amine neutralizing agent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906793A (en) * | 2016-06-25 | 2016-08-31 | 成都杰晟蜀邦新材料科技有限公司 | Water-based unsaturated polyester resin and preparation method thereof |
| CN107245129A (en) * | 2017-08-07 | 2017-10-13 | 南方医科大学 | A kind of hydrophilic unsaturated aliphatic polyester and its preparation method and application |
| CN109957300A (en) * | 2017-12-14 | 2019-07-02 | 惠州市长润发涂料有限公司 | A kind of preparation method of more official's polyester acrylates |
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|---|---|---|---|---|
| EP0711791A1 (en) * | 1994-11-08 | 1996-05-15 | Elf Atochem S.A. | Blends of polymers containing a halogenated polymer compatibilized with a graft aliphatic polyester |
| WO2003010254A2 (en) * | 2001-07-26 | 2003-02-06 | Ucb, S.A. | Unsaturated powder coating compositions |
| CN101861341A (en) * | 2007-09-18 | 2010-10-13 | 库克复合材料和聚合物公司 | The thermoset composition of the low VOC of the polyester acrylic resin that gel coating is used |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0711791A1 (en) * | 1994-11-08 | 1996-05-15 | Elf Atochem S.A. | Blends of polymers containing a halogenated polymer compatibilized with a graft aliphatic polyester |
| WO2003010254A2 (en) * | 2001-07-26 | 2003-02-06 | Ucb, S.A. | Unsaturated powder coating compositions |
| CN101861341A (en) * | 2007-09-18 | 2010-10-13 | 库克复合材料和聚合物公司 | The thermoset composition of the low VOC of the polyester acrylic resin that gel coating is used |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906793A (en) * | 2016-06-25 | 2016-08-31 | 成都杰晟蜀邦新材料科技有限公司 | Water-based unsaturated polyester resin and preparation method thereof |
| CN107245129A (en) * | 2017-08-07 | 2017-10-13 | 南方医科大学 | A kind of hydrophilic unsaturated aliphatic polyester and its preparation method and application |
| CN107245129B (en) * | 2017-08-07 | 2019-04-02 | 南方医科大学 | A kind of hydrophilic unsaturated aliphatic polyester and its preparation method and application |
| CN109957300A (en) * | 2017-12-14 | 2019-07-02 | 惠州市长润发涂料有限公司 | A kind of preparation method of more official's polyester acrylates |
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| CN103030745B (en) | 2014-12-24 |
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