CN103030745B - 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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- CN103030745B CN103030745B CN201210523769.2A CN201210523769A CN103030745B CN 103030745 B CN103030745 B CN 103030745B CN 201210523769 A CN201210523769 A CN 201210523769A CN 103030745 B CN103030745 B CN 103030745B
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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 ultraviolet light polymerization characteristic.
Background technology
After the 6O age in 20th century, Bayer company of Germany developed first-generation ultraviolet-curing paint (UVCC), because this technology meets 3E principle completely, have that curing speed is fast, non-volatility solvent, save energy, expense are low, can the feature such as automatic production, remain always and develop fast.The main component used due to photo-cured coating system and oligopolymer generally have higher viscosity, must add more reactive thinner before use to regulate viscosity, to improve rheological, and these reactive thinner major parts have toxicity and pungency; On the other hand, along with the raising gradually of people's environmental consciousness and the increasingly strict of various countries' environmental regulation, water-borne coatings is one of Main way becoming paint development, and its low-viscosity very easily regulated makes it to be suitable for spraying.In this case, UV solidified aqueous coating arises at the historic moment, and it combines both advantages, becomes research and development field very active at present.Unsaturated polyester resin (UPR) has excellent mechanical property, electrical property and resistance to chemical corrosion, and complete processing is easy, so Abroad in Recent Years development is comparatively rapid, is develop one of kind faster in thermosetting resin.Be widely used in the fields such as industry, agricultural, traffic and transport.Therefore, the study on the synthesis of photocuring water-based unsaturated polyester be society and market economy development needed for, there is higher using value.
The O of ground state
2be diradical in essence, therefore have the living radical produced in light-initiated process and stronger add Viability, form more stable peroxylradicals.This process rate is very fast, can compete mutually, show most the inhibition of polymerization process with the addition reaction of living radical to monomer.Oxygen inhibition is very large to the harm of UV solidification process, especially when coating thickness is thinner.The oxygen molecule not only dissolved in formula system hinders polymerization, and in light-initiated process, along with the consumption of oxygen molecule in curing system, the oxygen in coatingsurface air also can diffuse to rapidly in solidified coating, continues to hinder polymerization.The oxygen constantly diffusing to coat inside from the external world is the major cause hindering polymerization.In the shallow top layer that oxygen inhibition also the most easily occurs in coating or whole comparatively shallow layer, because in these regions, the oxygen molecule diffusion in environment is easier.
In atmosphere during photocuring, oxygen inhibition effect usually causes coating bottom to solidify, surface is uncured and the situation of stickness.Oxygen inhibition finally can cause coating top layer to occur the oxidisability structures such as great amount of hydroxy group, carbonyl, peroxy, thus affects the permanent stability of coating, even may affect the performances such as the hardness of the rear paint film of solidification, glossiness and resistance to marring.
Summary of the invention
The object of this invention is to provide a kind of aqueous photo-curing unsaturated polyester and preparation method thereof, polyester prepared by the method has the feature of good stability.
To achieve these goals, the technical solution used in the present invention is: aqueous photo-curing unsaturated polyester, it is characterized in that its chemical structural formula is:
In formula (1): R
1for H or CH
3; R
2for H or CH
3; R
3for
r
4for
or
wherein p
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.
By such scheme, q1+q2=p, p=2 or 3.
Preparation method's (adopting one of method of mass polymerization) of above-mentioned aqueous photo-curing unsaturated polyester, it is characterized in that: it comprises the following steps: 1) under the protection of nitrogen, be the polyol blends of 40-60 by mass parts, the polyprotonic acid mixture of 40-60 mass parts, the oxidation inhibitor of 0.1-0.3 mass parts joins with in the four mouthfuls of reactors stirred, and adopts mass polymerization;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. dimethylol propionic acid three kinds of raw material compositions, wherein TriMethylolPropane(TMP) mono allyl ether accounts for the 33%-82.5%(mass parts of polyol blends quality is 20-33), shared by dimethylol propionic acid, the 16.6-45%(mass parts of polyol blends quality is 10-18);
2. and unsaturated dibasic acid or the unsaturated acid anhydride containing carbon-carbon double bond (not comprising phenyl ring) described polyprotonic acid mixture is made up of following two kinds of raw materials: a kind of or two kinds of mixing by any proportioning 1. in monounsaturated dicarboxylic acid or saturated (comprise containing phenyl ring) acid anhydrides; Wherein, the 16.6-52.5%(mass parts of polyprotonic acid mixture quality shared by unsaturated dibasic acid or the unsaturated acid anhydride containing carbon-carbon double bond (not comprising phenyl ring) is 10-21);
2) be warming up to 140 DEG C, insulation 1h, then be warming up to 150 DEG C, under this state of insulation 1h(, keep backflow, not draining); Then be warming up to 180 DEG C with 1h, and be incubated 2h(and keep reaction at this temperature) after, then keep 0.5-1h to dewater under vacuum tightness 0.040MPa; Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches the theoretical value (this theoretical value has different theories value according to formulating of recipe) of formulating of recipe;
3) be cooled to 150 DEG C, and add the stopper of 0.2-0.5 mass parts, continue to be cooled to 95 DEG C; The glycidyl methacrylate dripping 7-15 mass parts adds in reactor, and adds 0.1-0.3 mass parts Tetramethylammonium iodide; React at this temperature to acid number and reach the theoretical value (this theoretical value has different theories value according to formulating of recipe) of formulating of recipe; Be cooled to 65 DEG C, adding the pH value that neutralizing agent is neutralized to product is 7-8, obtains product (i.e. unsaturated polyester); Product stirs and adds water dilution (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 aqueous photo-curing unsaturated polyester.
Preparation method's (adopting the method two of mass polymerization) of above-mentioned aqueous photo-curing unsaturated polyester, it is characterized in that: it comprises the following steps: 1. under the protection of nitrogen, be the polyol blends of 40-60 by mass parts, the polyprotonic acid mixture of 35-55 mass parts, the oxidation inhibitor of 0.1-0.3 mass parts joins with in the four mouthfuls of reactors stirred, and adopts mass polymerization;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. dimethylol propionic acid three kinds of raw material compositions, wherein TriMethylolPropane(TMP) mono allyl ether accounts for the 33%-82.5%(mass parts of polyol blends quality is 20-33), shared by dimethylol propionic acid, the 16.6-45%(mass parts of polyol blends quality is 10-18);
2. and unsaturated dibasic acid or the unsaturated acid anhydride containing carbon-carbon double bond (not comprising phenyl ring) described polyprotonic acid mixture is made up of following two kinds of raw materials: a kind of or two kinds of mixing by any proportioning 1. in monounsaturated dicarboxylic acid or saturated (comprise containing phenyl ring) acid anhydrides; Wherein, the 8.5%-27.5%(mass parts of polyprotonic acid mixture quality shared by unsaturated dibasic acid or the unsaturated acid anhydride containing carbon-carbon double bond (not comprising phenyl ring) is 5-11);
2. be warming up to 140 DEG C, insulation 1h, then be warming up to 150 DEG C, under this state of insulation 1h(, keep backflow, not draining); Then 180 DEG C are warming up to 1h, add the unsaturated acid of 5-10 mass parts or the unsaturated acid anhydride containing carbon-carbon double bond (not comprising phenyl ring) again, and be incubated 2h(and keep reaction at this temperature) after, then keep 0.5-1h to dewater under vacuum tightness 0.040MPa; Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches the theoretical value (this theoretical value has different theories value according to formulating of recipe) of formulating of recipe;
3. be cooled to 150 DEG C, and add the stopper of 0.2-0.5 mass parts, continue to be cooled to 95 DEG C; The glycidyl methacrylate dripping 7-15 mass parts enters in reactor, and adds 0.1-0.3 mass parts Tetramethylammonium iodide, reacts to acid number and reach the theoretical value (this theoretical value has different theories value according to formulating of recipe) of formulating of recipe at this temperature; Be cooled to 65 DEG C, adding the pH value that neutralizing agent is neutralized to product is 7-8, obtains product (i.e. unsaturated polyester); Product stirs and adds water dilution (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 aqueous photo-curing unsaturated polyester.
By such scheme, polyvalent alcohol is propylene glycol, ethylene glycol, hexylene glycol, glycol ether, dipropylene glycol or neopentyl glycol etc.
By such scheme, described monounsaturated dicarboxylic acid is the mixing of any one or any two or more in hexanodioic acid, suberic acid, succinic acid, propanedioic acid, pentanedioic acid etc. by any proportioning; Described saturated (comprise containing 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.; Unsaturated acid anhydride containing carbon-carbon double bond (not comprising phenyl ring) is maleic anhydride.
By such scheme, described oxidation inhibitor is triphenyl phosphite.
By such scheme, described stopper selects any one or any two or more in Resorcinol, methyl hydroquinone, para benzoquinone, tertiary butyl catechol, 2,6-di-tert-butyl-4-cresols etc. by the mixing of any proportioning.
By such scheme, described neutralizing agent is organic amine neuutralizer (N, N--dimethylethanolamine).
End-use: aqueous photo-curing unsaturated polyester of the present invention may be used for woodwork coating, has higher using value at woodenware and wood finishing field.Because aqueous photo-curing unsaturated polyester (resin) dilute with water of the present invention avoids solvent and reactive thinner to the injury of human contact, achieve low VOC, be easy to the recovery reprocessing of paper simultaneously, and can gloss oil for paper be applied to.The present invention also may be used for other can not the field of high temperature film forming, such as: Electronic Packaging, tackiness agent, printing board material, electronic industry etc.
The invention has the beneficial effects as follows: polyester prepared by the method has good stability, water-fast good, curing speed is fast, glossiness is high feature.
Embodiment
Illustrate content of the present invention further by the following examples, but content of the present invention is not only confined to the following examples.Embodiment 1(adopts one of method of mass polymerization):
Preparation method's (one of mass polymerization) of aqueous photo-curing unsaturated polyester, it comprises the following steps:
1. under the protection of nitrogen, by 33.00g TriMethylolPropane(TMP) mono allyl ether, 9.23g neopentyl glycol (for polyvalent alcohol), 17.53g dimethylol propionic acid, 14.77g Tetra hydro Phthalic anhydride (for saturated (comprise containing phenyl ring) acid anhydrides), 10.15g maleic anhydride [unsaturated acid anhydride for containing carbon-carbon double bond (not comprising phenyl ring)], 15.84g hexanodioic acid (for monounsaturated dicarboxylic acid), and 0.26g oxidation inhibitor (triphenyl phosphite) joins with agitator, prolong, in four mouthfuls of reactors of thermometer and dropper, adopt mass polymerization.
2. be warming up to 140 DEG C, insulation 1h, then be warming up to 150 DEG C, under this state of insulation 1h(, keep backflow, not draining).Then be warming up to 180 DEG C with 1h, and be incubated 2h, and keep reaction at this temperature, then keep 0.5-1h to dewater under vacuum tightness 0.040MPa.Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches 80.
3. be cooled to 150 DEG C, and add 0.30g stopper, continue to be cooled to 95 DEG C.Drip 14.5g glycidyl methacrylate (GMA) to enter in reactor, and add 0.30g Tetramethylammonium iodide, half an hour drips off.React to acid number to 20 at this temperature.Be cooled to 65 DEG C, and add 3g neutralizing agent and carry out neutralizing (pH value to product is 7-8), obtain product (i.e. unsaturated polyester), the quality of product is 110g, 15min is stirred 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).
This tests oxidation inhibitor used is triphenyl phosphite.
This tests stopper used is Resorcinol.
This tests neutralizing agent used is N, N-dimethylethanolamine.
The hardness test of this experiment adopts the method test of pencil hardometer, and test result sees the following form.
The water-fast test of this experiment carries out in 25 DEG C of water, non-foaming with film, and nondiscoloration, do not come off for criterion of acceptability, test result sees the following form.
Storage stability is placed in vial at normal temperatures, not stratified with resin solution, does not change color as 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 | Micro-Huang, transparent (glossiness is high) |
| Solid content | 43.1wt%(large arch dam) |
| PH value (after dilution) | 8 |
| Acid number (solid part) | 20 |
| Number-average molecular weight | 900 |
| Hardness | 1h |
| Water-fast (25 DEG C) | 72h is unchanged |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 1 illustrates: polyester prepared by the method has good stability, large arch dam, curing speed fast (2500w high voltage mercury lamp 20s fast filming), feature that glossiness is high.
Embodiment 2(adopts the method two of mass polymerization):
Preparation method's (adopting the method two of mass polymerization) of aqueous photo-curing unsaturated polyester, it comprises the following steps:
1. under the protection of nitrogen; by 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 four mouthfuls of reactors with agitator, prolong, thermometer and dropper, adopt mass polymerization.
2. be warming up to 140 DEG C, insulation 1h, then be warming up to 150 DEG C, under this state of insulation 1h(, keep backflow, not draining).Then be warming up to 180 DEG C with 1h, then add 9.00g maleic anhydride, and be incubated 2h, and after keeping reaction at this temperature, then under vacuum tightness 0.040MPa, keep 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 DEG C, and add 0.32g stopper, continue to be cooled to 95 DEG C.Drip 8.00g glycidyl methacrylate (GMA) to enter in reactor, and add 0.22g Tetramethylammonium iodide (catalyzer).React to acid number to 22 at this temperature.Be cooled to 65 DEG C, and add 2.40g neutralizing agent and carry out neutralizing (pH value to product is 7-8), obtain product (i.e. unsaturated polyester), the quality of product is 90g, 15min is stirred 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).
This tests oxidation inhibitor used is triphenyl phosphite.
This tests stopper used is Resorcinol.
This tests neutralizing agent used is N, N-dimethylethanolamine.
The hardness test of this experiment adopts the method test of pencil hardometer, and test result sees the following form.
The water-fast test of this experiment carries out in 25 DEG C of water, non-foaming with film, and nondiscoloration, do not come off for criterion of acceptability, test result sees the following form.
Storage stability is placed in vial at normal temperatures, not stratified with resin solution, does not change color as 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 | Micro-Huang, transparent |
| Solid content | 33.3% |
| PH value (after dilution) | 8 |
| Acid number (solid part) | 22 |
| Number-average molecular weight | 2300 |
| Hardness | 3h(hardness is high) |
| Water-fast (25 DEG C) | 120h unchanged (water-fast good) |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 2 illustrates: polyester prepared by the method has that hardness is high, good stability, water-fast good, curing speed fast (2500w high voltage mercury lamp 20s fast filming), feature that glossiness is high.
Embodiment 3(adopts one of method of mass polymerization):
Preparation method's (adopting one of method of mass polymerization) of aqueous photo-curing unsaturated polyester, it comprises the following steps:
1. under the protection of nitrogen; by 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 four mouthfuls of reactors with agitator, prolong, thermometer and dropper, adopt mass polymerization.
2. be warming up to 140 DEG C, insulation 1h, then be warming up to 150 DEG C, under this state of insulation 1h(, keep backflow, not draining).Then be warming up to 180 DEG C with 1h, and be incubated 2h, and after keeping reaction at this temperature, then keep 0.5-1h to dewater under vacuum tightness 0.040MPa.Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches 150.
3. be cooled to 150 DEG C, and add 0.30g stopper, continue to be cooled to 95 DEG C.Drip 14g glycidyl methacrylate (GMA) to enter in reactor, and add 0.30g Tetramethylammonium iodide, half an hour drips off.React to acid number to 80 at this temperature.Be cooled to 65 DEG C, and add 10gN, N-dimethylethanolamine neutralizing agent carries out neutralizing (pH value to product is 7-8), obtain product (i.e. 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 aqueous photo-curing unsaturated polyester.
This tests oxidation inhibitor used is triphenyl phosphite.
This tests stopper used is Resorcinol.
This tests neutralizing agent used is N, N-dimethylethanolamine.
The hardness test of this experiment adopts the method test of pencil hardometer, and test result sees the following form.
The water-fast test of this experiment carries out in 25 DEG C of water, non-foaming with film, and nondiscoloration, do not come off for criterion of acceptability, test result sees the following form.
Storage stability is placed in vial at normal temperatures, not stratified with resin solution, does not change color as 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 | Micro-Huang, transparent |
| Solid content | 40% |
| PH value (after 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 illustrates: polyester prepared by the method has good stability, solid containing higher, water-fast good, curing speed fast (2500w high voltage mercury lamp 20s fast filming), feature that glossiness is high.
Embodiment 4
Substantially the same manner as Example 1, difference is: " neopentyl glycol " is replaced by " propylene glycol "; " hexanodioic acid " is replaced by " suberic acid "; " Resorcinol " is 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 " is replaced by " ethylene glycol "; " hexanodioic acid " is replaced by " succinic acid "; " Resorcinol " is 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 " is replaced by " hexylene glycol "; " hexanodioic acid " is replaced by " propanedioic acid "; " Resorcinol " is 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 " is replaced by " glycol ether "; " hexanodioic acid " is replaced by " pentanedioic acid "; " Resorcinol " is 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 " is replaced by " dipropylene glycol "; " Resorcinol " is 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
Preparation method's (adopting one of method of mass polymerization) of aqueous photo-curing unsaturated polyester, it comprises the following steps: 1) under the protection of nitrogen, by the polyol blends of 60g, the polyprotonic acid mixture of 60g, the oxidation inhibitor of 0.3g joins with in the four mouthfuls of reactors stirred, and adopts mass polymerization;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. dimethylol propionic acid three kinds of raw material compositions, wherein TriMethylolPropane(TMP) mono allyl ether accounts for 82.5% of polyol blends quality, 16.6% of polyol blends quality shared by dimethylol propionic acid;
Described polyprotonic acid mixture is made up of following two kinds of raw materials: 1. saturated (comprise containing phenyl ring) acid anhydrides, the unsaturated acid anhydride 2. and containing carbon-carbon double bond (not comprising phenyl ring); Wherein, 52.5% of polyprotonic acid mixture quality shared by the unsaturated acid anhydride containing carbon-carbon double bond (not comprising phenyl ring);
Described polyvalent alcohol is propylene glycol.Saturated (comprise containing phenyl ring), acid anhydrides was Tetra hydro Phthalic anhydride.Unsaturated acid anhydride containing carbon-carbon double bond (not comprising phenyl ring) is maleic anhydride.Described oxidation inhibitor is triphenyl phosphite.
2) be warming up to 140 DEG C, insulation 1h, then be warming up to 150 DEG C, under this state of insulation 1h(, keep backflow, not draining); Then be warming up to 180 DEG C with 1h, and be incubated 2h(and keep reaction at this temperature) after, then keep 0.5-1h to dewater under vacuum tightness 0.040MPa; Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches the theoretical value 168 of formulating of recipe;
3) be cooled to 150 DEG C, and add the stopper of 0.5g, continue to be cooled to 95 DEG C; The glycidyl methacrylate dripping 15g adds in reactor, and adds 0.3g Tetramethylammonium iodide; React at this temperature to acid number and reach the theoretical value 100 of formulating of recipe; Be cooled to 65 DEG C, adding the pH value that 12g neutralizing agent is neutralized to product is 7-8, obtains product (i.e. unsaturated polyester); Product stirs and adds water dilution (high-speed stirring 15min-30min, the rotating speed of described high-speed stirring is 800-1200 rev/min), and the add-on of water is 100% of product (being equivalent to whole unsaturated polyester) quality, namely obtains aqueous photo-curing unsaturated polyester.
Resorcinol selected by described stopper.Described neutralizing agent is organic amine neuutralizer (N, N-dimethylethanolamine).
The hardness test of this experiment adopts the method test of pencil hardometer, and test result sees the following form.
The water-fast test of this experiment carries out in 25 DEG C of water, non-foaming with film, and nondiscoloration, do not come off for criterion of acceptability, test result sees the following form.
Storage stability is placed in vial at normal temperatures, not stratified with resin solution, does not change color as 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 | Micro-Huang, transparent (glossiness is high) |
| Solid content | 50wt% |
| PH value (after dilution) | 8 |
| Acid number (solid part) | 100 |
| Number-average molecular weight | 900 |
| Hardness | 1h |
| Water-fast (25 DEG C) | 48h is unchanged |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 4 illustrates: polyester prepared by the method has good stability, large arch dam, curing speed fast (2500w high voltage mercury lamp 20s fast filming), feature that glossiness is high.
Embodiment 10
Preparation method's (adopting one of method of mass polymerization) of aqueous photo-curing unsaturated polyester, it comprises the following steps: 1) under the protection of nitrogen, by the polyol blends of 40g, the polyprotonic acid mixture of 40g, the oxidation inhibitor of 0.1g joins with in the four mouthfuls of reactors stirred, and adopts mass polymerization;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. polyvalent alcohol and 3. dimethylol propionic acid three kinds of raw material compositions, wherein TriMethylolPropane(TMP) mono allyl ether accounts for 33% of polyol blends quality, 45% of polyol blends quality shared by dimethylol propionic acid;
2. and unsaturated dibasic acid described polyprotonic acid mixture is made up of following two kinds of raw materials: 1. monounsaturated dicarboxylic acid; Wherein, polyprotonic acid mixture quality shared by unsaturated dibasic acid 52.5%;
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 DEG C, insulation 1h, then be warming up to 150 DEG C, under this state of insulation 1h(, keep backflow, not draining); Then be warming up to 180 DEG C with 1h, and be incubated 2h(and keep reaction at this temperature) after, then keep 0.5-1h to dewater under vacuum tightness 0.040MPa; Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches the theoretical value 105 of formulating of recipe;
3) be cooled to 150 DEG C, and add the stopper of 0.2g, continue to be cooled to 95 DEG C; The glycidyl methacrylate dripping 7g adds in reactor, and adds 0.1g Tetramethylammonium iodide; React at this temperature to acid number and reach the theoretical value 70 of formulating of recipe; Be cooled to 65 DEG C, adding the pH value that neutralizing agent is neutralized to product is 7-8, obtains product (i.e. unsaturated polyester); Product stirs and adds water dilution (high-speed stirring 15min-30min, the rotating speed of described high-speed stirring is 800-1200 rev/min), and the add-on of water is 200% of product (being equivalent to whole unsaturated polyester) quality, namely obtains aqueous photo-curing unsaturated polyester.
Resorcinol selected by described stopper.Described neutralizing agent is organic amine neuutralizer (N, N-dimethylethanolamine).
The hardness test of this experiment adopts the method test of pencil hardometer, and test result sees the following form.
The water-fast test of this experiment carries out in 25 DEG C of water, non-foaming with film, and nondiscoloration, do not come off for criterion of acceptability, test result sees the following form.
Storage stability is placed in vial at normal temperatures, not stratified with resin solution, does not change color as 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 | Micro-Huang, transparent (glossiness is high) |
| Solid content | 33wt% |
| PH value (after dilution) | 8 |
| Acid number (solid part) | 70 |
| Number-average molecular weight | 2800 |
| Hardness | 3h(hardness is high) |
| Water-fast (25 DEG C) | 120h unchanged (water-fast good) |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 5 illustrates: the feature that polyester prepared by the method has good stability, hardness is high, curing speed is fast (2500w high voltage mercury lamp 20s fast filming), glossiness is high.
Embodiment 12
Substantially the same manner as Example 1, difference is: " Tetra hydro Phthalic anhydride " is 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 " is replaced by " trimellitic acid 1,2-anhydride ".Technical target of the product is identical with embodiment 1.
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (8)
1. aqueous photo-curing unsaturated polyester, is characterized in that its chemical structural formula is:
In formula (1): R
1for H or CH
3; R
2for H or CH
3; R
3for
r
4for
or
wherein p
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: q
1+ q
2=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 comprises the following steps: 1) under the protection of nitrogen, be the polyol blends of 40-60 by mass parts, the polyprotonic acid mixture of 40-60 mass parts, the oxidation inhibitor of 0.1-0.3 mass parts joins with in the four mouthfuls of reactors stirred;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. propylene glycol, ethylene glycol, hexylene glycol, glycol ether, dipropylene glycol or neopentyl glycol and 3. dimethylol propionic acid three kinds of raw material compositions, wherein TriMethylolPropane(TMP) mono allyl ether accounts for the 33%-82.5% of polyol blends quality, the 16.6-45% of polyol blends quality shared by dimethylol propionic acid;
2. and unsaturated dibasic acid or unsaturated acid anhydride described polyprotonic acid mixture is made up of following two kinds of raw materials: a kind of or two kinds of mixing by any proportioning 1. in monounsaturated dicarboxylic acid or saturated acid anhydrides; Wherein, the 16.6-52.5% of polyprotonic acid mixture quality shared by unsaturated dibasic acid or unsaturated acid anhydride;
2) be warming up to 140 DEG C, insulation 1h, then be warming up to 150 DEG C, insulation 1h; Then 180 DEG C are warming up to 1h, and after being incubated 2h, then keep 0.5-1h to dewater under vacuum tightness 0.040MPa;
3) be cooled to 150 DEG C, and add the stopper of 0.2-0.5 mass parts, continue to be cooled to 95 DEG C; The glycidyl methacrylate dripping 7-15 mass parts adds in reactor, and adds 0.1-0.3 mass parts Tetramethylammonium iodide; Be cooled to 65 DEG C, adding the pH value that neutralizing agent is neutralized to product is 7-8, obtains product; Product stirs and adds water dilution, and the add-on of water is the 50%-200% of product quality, namely obtains 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 comprises the following steps: 1. under the protection of nitrogen, be the polyol blends of 40-60 by mass parts, the polyprotonic acid mixture of 35-55 mass parts, the oxidation inhibitor of 0.1-0.3 mass parts joins with in the four mouthfuls of reactors stirred;
Described polyol blends is by 1. TriMethylolPropane(TMP) mono allyl ether, 2. propylene glycol, ethylene glycol, hexylene glycol, glycol ether, dipropylene glycol or neopentyl glycol and 3. dimethylol propionic acid three kinds of raw material compositions, wherein TriMethylolPropane(TMP) mono allyl ether accounts for the 33%-82.5% of polyol blends quality, the 16.6-45% of polyol blends quality shared by dimethylol propionic acid;
2. and unsaturated dibasic acid or unsaturated acid anhydride described polyprotonic acid mixture is made up of following two kinds of raw materials: a kind of or two kinds of mixing by any proportioning 1. in monounsaturated dicarboxylic acid or saturated acid anhydrides; Wherein, the 8.5%-27.5% of polyprotonic acid mixture quality shared by unsaturated dibasic acid or unsaturated acid anhydride;
2. be warming up to 140 DEG C, insulation 1h, then be warming up to 150 DEG C, insulation 1h; Then be warming up to 180 DEG C with 1h, then add unsaturated acid or the unsaturated acid anhydride of 5-10 mass parts, and after being incubated 2h, then keep 0.5-1h to dewater under vacuum tightness 0.040MPa;
3. be cooled to 150 DEG C, and add the stopper of 0.2-0.5 mass parts, continue to be cooled to 95 DEG C; The glycidyl methacrylate dripping 7-15 mass parts enters in reactor, and adds 0.1-0.3 mass parts Tetramethylammonium iodide; Be cooled to 65 DEG C, adding the pH value that neutralizing agent is neutralized to product is 7-8, obtains product; Product stirs and adds water dilution, and the add-on of water is the 50%-200% of product quality, namely obtains aqueous photo-curing unsaturated polyester.
5. according to the preparation method of the aqueous photo-curing unsaturated polyester described in claim 3 or 4, it is characterized in that: described monounsaturated dicarboxylic acid is the mixing of any one or any two or more in hexanodioic acid, suberic acid, succinic acid, propanedioic acid, pentanedioic acid by 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.
6. according to the preparation method of the aqueous photo-curing unsaturated polyester described in claim 3 or 4, it is characterized in that: described oxidation inhibitor is triphenyl phosphite.
7. according to the preparation method of the aqueous photo-curing unsaturated polyester described in claim 3 or 4, it is characterized in that: described stopper selects any one or any two or more in Resorcinol, methyl hydroquinone, para benzoquinone, 2,6-di-tert-butyl-4-cresols by the mixing of any proportioning.
8. according to the preparation method of the aqueous photo-curing unsaturated polyester described in claim 3 or 4, it is characterized in that: described neutralizing agent is organic amine neuutralizer.
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| 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 |
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