CN103013304B - Method for preparation of water-based UV-curing unsaturated polyester by solvent azeotropy - Google Patents
Method for preparation of water-based UV-curing unsaturated polyester by solvent azeotropy Download PDFInfo
- Publication number
- CN103013304B CN103013304B CN201210521961.8A CN201210521961A CN103013304B CN 103013304 B CN103013304 B CN 103013304B CN 201210521961 A CN201210521961 A CN 201210521961A CN 103013304 B CN103013304 B CN 103013304B
- Authority
- CN
- China
- Prior art keywords
- acid
- mass parts
- product
- unsaturated polyester
- unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a synthesis method of water-based unsaturated polyester with a UV (ultraviolet) curing property. The method is characterized by comprising the steps of: 1) under protection of nitrogen, subjecting 40-60 parts by mass of a polyol mixture, 40-60 parts by mass of a polyacid mixture, 0.1-0.3 part by mass of an antioxidant and 4-8 parts by mass of an inert solvent to solvent azeotropy; 2) raising the temperature to 140DEG C, conducting thermal preservation for 1h, then raising the temperature again to 150DEG C, performing thermal preservation for 1h; and then raising the temperature to 180DEG C in 1h, and implementing thermal preservation for 2h; 3) lowering the temperature to 150DEG C, and adding 0.2-0.5 part by mass of a polymerization inhibitor; adding 7-15 parts by mass of glycidyl methacrylate into the reactor in a dropwise manner, and adding 0.1-0.3 part by mass of tetramethylammonium iodide; lowering the temperature to 65DEG C, adding a neutralizer for neutralization till a product with a PH value of 7-8; and stirring the product, and adding water to dilute the product, with the added water accounting for 50%-200% of the mass of the product, thus obtaining the water-based UV-curing unsaturated polyester. The polyester prepared by the method provided in the invention has the characteristics of good stability and the like.
Description
Technical field
The present invention relates to the synthetic method that a class has the water-based unsaturated polyester of 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 method that solvent azeotropic prepares aqueous photo-curing unsaturated polyester, polyester prepared by the method has the feature of good stability.
To achieve these goals, the technical solution used in the present invention is: solvent azeotropic prepares the method (adopting one of method of solvent azeotropic method) of 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 and the inert solvent (such as: toluene, dimethylbenzene etc.) of 4-8 mass parts join with in the four mouthfuls of reactors stirred, and adopt solvent azeotropic method;
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);
Described inert solvent is toluene or dimethylbenzene etc.;
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); Under vacuum tightness 0.040MPa, 0.5-1h is kept to dewater again; 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; React at this temperature and reach the theoretical value (this theoretical value has different theories value according to formulating of recipe) of formulating of recipe to acid number, under vacuum tightness is 0.050-0.080MPa, then keeps the water that 0.5-1.5h(removes inert solvent and may not drain); 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 that product (is equivalent to whole unsaturated polyester
)the 50%-200% of quality, namely obtains aqueous photo-curing unsaturated polyester.
Solvent azeotropic prepares the method (adopting the method two of solvent azeotropic method) of 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 and the inert solvent (such as: toluene, dimethylbenzene etc.) of 4-8 mass parts join with in the four mouthfuls of reactors stirred, and adopt 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);
Described inert solvent is toluene or dimethylbenzene etc.;
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), 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; Then under vacuum tightness is 0.050-0.080MPa, the water that 0.5-1.5h(removes inert solvent and may not drain is kept); 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 that product (is equivalent to whole unsaturated polyester
)the 50%-200% of 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 or 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 solvent azeotropic method):
Solvent azeotropic prepares the method (adopting one of method of solvent azeotropic method) of aqueous photo-curing unsaturated polyester, and 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; 15.00g suberic acid (monounsaturated dicarboxylic acid); 12.00g maleic anhydride [unsaturated acid anhydride for containing carbon-carbon double bond (not comprising phenyl ring)]; 15.00g hexanodioic acid (for monounsaturated dicarboxylic acid), 0.26g oxidation inhibitor and 5g dimethylbenzene join in four mouthfuls of reactors with agitator, prolong, thermometer and dropper.
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), increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches 82.
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.Then under vacuum tightness 0.070MPa, keep 0.5-1h dehydration desolventizing; 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; Product stirs and adds 150g water dilution (stirring 15min under the speed of 800r/min), namely obtains 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 1 is as shown in table 1:
Table 1
| Outward appearance | Micro-Huang, transparent (glossiness is high) |
| Solid content | 42wt%(large arch dam) |
| PH value (after dilution) | 8 |
| Acid number (solid part) | 20 |
| Number-average molecular weight | 1100 |
| Hardness | 1h |
| Water-fast (25 DEG C) | 96h is unchanged |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 1 illustrates: polyester prepared by the method has good stability, solid containing higher, curing speed fast (2500w high voltage mercury lamp 20s fast filming), feature that glossiness is high.
Embodiment 2:
Solvent azeotropic prepares the method (adopting the method two of solvent azeotropic method) of aqueous photo-curing unsaturated polyester, and it comprises the following steps:
1) under the protection of nitrogen; by 20.00g TriMethylolPropane(TMP) mono allyl ether; 10.00g neopentyl glycol; 12.00g dimethylol propionic acid; 11.00g suberic acid; 9.00g maleic anhydride, 15.00g hexanodioic acid, 0.26g oxidation inhibitor and 6g dimethylbenzene join in four mouthfuls of reactors with agitator, prolong, thermometer and dropper.
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 keeping reaction at this temperature); Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches 110.
3) be cooled to 150 DEG C, and add 0.30g stopper, continue to be cooled to 95 DEG C.Drip 8.00g 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.Then under vacuum tightness 0.070MPa, keep 0.5h dehydration desolventizing.Be cooled to 65 DEG C, and add 6.0g neutralizing agent and carry out neutralizing (pH value to product is 7-8), obtain product (i.e. unsaturated polyester
),the quality of product is 95g.Stir 15min under the speed of 800r/min, then slowly add 180g water dilution (high-speed stirring half an hour), namely obtain 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:
Table 2
| Outward appearance | Micro-Huang, transparent (glossiness is high) |
| Solid content | 34.5wt% |
| PH value (after dilution) | 8 |
| Acid number (solid part) | 80 |
| Number-average molecular weight | 2000 |
| Hardness | 2h |
| Water-fast (25 DEG C) | 96h is unchanged |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 2 illustrates: polyester prepared by the method has good stability, water-fast good, curing speed fast (2500w high voltage mercury lamp 20s fast filming), feature that glossiness is high.
Embodiment 3:
Solvent azeotropic prepares the method (adopting one of method of solvent azeotropic method) of aqueous photo-curing unsaturated polyester, and it comprises the following steps:
1) under the protection of nitrogen; by 20.00g TriMethylolPropane(TMP) mono allyl ether; 14.50g neopentyl glycol; 9.00g dimethylol propionic acid; 16.50g suberic acid; 15.00g maleic anhydride, 15.00g hexanodioic acid, 0.26g oxidation inhibitor and 6g dimethylbenzene join in four mouthfuls of reactors with agitator, prolong, thermometer and dropper.
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).Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches 90.
3) be cooled to 150 DEG C, and add 0.30g stopper, continue to be cooled to 95 DEG C.Drip 10g glycidyl methacrylate (GMA) to enter in reactor, and add 0.30g Tetramethylammonium iodide (half an hour drips off), react to acid number to 50 at this temperature.Then under vacuum tightness 0.070MPa, keep 0.5-1h dehydration desolventizing; Be cooled to 65 DEG C, and add 5g 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; Product stirs and adds the dilution of 200g water, stirs 15min, namely obtain aqueous photo-curing unsaturated polyester under the speed of 800r/min.
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:
Table 3
| Outward appearance | Micro-Huang, transparent (glossiness is high) |
| Solid content | 31wt% |
| PH value (after dilution) | 8 |
| Acid number (solid part) | 50 |
| Number-average molecular weight | 2800 |
| Hardness | 3h |
| Water-fast (25 DEG C) | 120h is unchanged |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 3 illustrates: polyester prepared by the method has good stability, 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 and suberic acid " is replaced by " succinic 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 and suberic acid " is replaced by " propanedioic 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 and suberic acid " is replaced by " pentanedioic 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 " Tetra hydro Phthalic anhydride [for saturated (comprise containing phenyl ring) acid anhydrides] "; " 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
Substantially the same manner as Example 1, difference is: " dimethylbenzene " is replaced by " toluene ".Technical target of the product is identical with embodiment 1.
embodiment 10
Solvent azeotropic prepares the method (adopting one of method of solvent azeotropic method) of aqueous photo-curing unsaturated polyester, and it comprises the following steps:
1) under the protection of nitrogen, be the polyol blends of 40 by mass parts, the polyprotonic acid mixture of 40 mass parts, the oxidation inhibitor of 0.1 mass parts and the inert solvent (such as: toluene) of 4 mass parts join with in the four mouthfuls of reactors stirred, and adopt solvent azeotropic method;
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 16.6%;
Polyvalent alcohol is propylene glycol; Described monounsaturated dicarboxylic acid is suberic acid; Unsaturated dibasic acid is fumaric acid;
By such scheme, 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); Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches the theoretical value 100 of formulating of recipe;
3) be cooled to 150 DEG C, and add the stopper of 0.2 mass parts, continue to be cooled to 95 DEG C; The glycidyl methacrylate dripping 7 mass parts enters in reactor, and adds 0.1 mass parts Tetramethylammonium iodide; React at this temperature and reach the theoretical value 70 of formulating of recipe to acid number, under vacuum tightness 0.070MPa, then keep 0.5-1h to dewater desolventizing; 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, the rotating speed of described high-speed stirring is 800 revs/min), and the add-on of water is that product (is equivalent to whole unsaturated polyester
)50% of quality, namely obtains aqueous photo-curing unsaturated polyester.
Resorcinol selected by described stopper.
By such scheme, 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 | 65wt%(large arch dam) |
| PH value (after dilution) | 8 |
| Acid number (solid part) | 70 |
| 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 11
Solvent azeotropic prepares the method (adopting one of method of solvent azeotropic method) of aqueous photo-curing unsaturated polyester, and it comprises the following steps:
1) under the protection of nitrogen, be the polyol blends of 60 by mass parts, the polyprotonic acid mixture of 60 mass parts, the oxidation inhibitor of 0.3 mass parts and the inert solvent (such as: dimethylbenzene) of 8 mass parts join with in the four mouthfuls of reactors stirred, and adopt solvent azeotropic method;
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 acid anhydrides, 2. unsaturated acid anhydride; Wherein, polyprotonic acid mixture quality shared by unsaturated acid anhydride 52.5%;
Polyvalent alcohol is propylene glycol; Described saturated acid anhydrides is Tetra hydro Phthalic anhydride; Unsaturated acid anhydride 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); Increasing nitrogen amount that can be suitable is beneficial to draining, reacts to acid number and reaches the theoretical value 150 of formulating of recipe;
3) be cooled to 150 DEG C, and add the stopper of 0.5 mass parts, continue to be cooled to 95 DEG C; The glycidyl methacrylate dripping 15 mass parts enters in reactor, and adds 0.3 mass parts Tetramethylammonium iodide; React at this temperature and reach the theoretical value 100 of formulating of recipe to acid number, under vacuum tightness is 0.08MPa, then keeps the water that 1.5h(removes inert solvent and may not drain); 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 30min, the rotating speed of described high-speed stirring is 1200 revs/min), and the add-on of water is that product (is equivalent to whole unsaturated polyester
)200% of quality, namely obtains aqueous photo-curing unsaturated polyester.
Resorcinol selected by described stopper.
By such scheme, 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) | 100 |
| Number-average molecular weight | 1000 |
| Hardness | 1h |
| Water-fast (25 DEG C) | 72h is unchanged |
| Storage stability (normal temperature) | 180 days unchanged (good stability) |
Watch 5 illustrates: polyester prepared by the method has good stability, curing speed fast (2500w high voltage mercury lamp 20s fast filming), feature that glossiness is high.
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 (6)
1. solvent azeotropic prepares the method for 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 and the inert solvent of 4-8 mass parts join 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;
Described inert solvent is toluene or dimethylbenzene;
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, and be incubated 2h; Under vacuum tightness 0.040MPa, 0.5-1h is kept to dewater again;
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; Then under vacuum tightness is 0.050-0.080MPa, 0.5-1.5h is kept; 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.
2. solvent azeotropic prepares the method for 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 and the inert solvent of 4-8 mass parts join 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%-42.9% of polyprotonic acid mixture quality shared by unsaturated dibasic acid or unsaturated acid anhydride;
Described inert solvent is toluene or dimethylbenzene;
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 be 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; Then under vacuum tightness is 0.050-0.080MPa, 0.5-1.5h is kept; 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.
3. solvent azeotropic according to claim 1 and 2 prepares the method for aqueous photo-curing unsaturated polyester, 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, trimellitic acid 1,2-anhydride; Unsaturated dibasic acid is toxilic acid or fumaric acid; Unsaturated acid anhydride is maleic anhydride.
4. solvent azeotropic according to claim 1 and 2 prepares the method for aqueous photo-curing unsaturated polyester, it is characterized in that, described oxidation inhibitor is triphenyl phosphite.
5. solvent azeotropic according to claim 1 and 2 prepares the method for aqueous photo-curing unsaturated polyester, it is characterized in that, 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 by the mixing of any proportioning.
6. solvent azeotropic according to claim 1 and 2 prepares the method for aqueous photo-curing unsaturated polyester, it is characterized in that, described neutralizing agent is organic amine neuutralizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210521961.8A CN103013304B (en) | 2012-12-07 | 2012-12-07 | Method for preparation of water-based UV-curing unsaturated polyester by solvent azeotropy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210521961.8A CN103013304B (en) | 2012-12-07 | 2012-12-07 | Method for preparation of water-based UV-curing unsaturated polyester by solvent azeotropy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103013304A CN103013304A (en) | 2013-04-03 |
| CN103013304B true CN103013304B (en) | 2015-05-06 |
Family
ID=47962433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210521961.8A Expired - Fee Related CN103013304B (en) | 2012-12-07 | 2012-12-07 | Method for preparation of water-based UV-curing unsaturated polyester by solvent azeotropy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103013304B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669962B (en) * | 2016-03-16 | 2018-01-12 | 无锡海特圣大光电材料科技有限公司 | A kind of preparation method of UV curing powder coating resin |
| 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 |
| CN109957096A (en) * | 2017-12-25 | 2019-07-02 | 宜兴市兴南复合材料厂有限公司 | A kind of pultrusion unsaturated-resin and preparation process |
| CN111072882A (en) * | 2019-12-31 | 2020-04-28 | 深圳市安品有机硅材料有限公司 | Modified waterborne polyurethane resin, coating and preparation method thereof |
| CN113861402B (en) * | 2021-10-27 | 2023-07-21 | 江苏富琪森新材料有限公司 | Water-based polyester resin and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2726568B1 (en) * | 1994-11-08 | 1996-12-06 | Atochem Elf Sa | POLYMER MIXTURES COMPRISING A HALOGEN POLYMER AND COMPATIBILIZED BY A GRAFT ALIPHATIC POLYESTER |
| WO2003010254A2 (en) * | 2001-07-26 | 2003-02-06 | Ucb, S.A. | Unsaturated powder coating compositions |
| US8546486B2 (en) * | 2007-09-18 | 2013-10-01 | Ccp Composites Us Llc | Low VOC thermosetting polyester acrylic resin for gel coat |
-
2012
- 2012-12-07 CN CN201210521961.8A patent/CN103013304B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103013304A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103059285B (en) | Method of preparing aqueous light-cured nonsaturated polyester by melting and then azeotropy | |
| CN103013304B (en) | Method for preparation of water-based UV-curing unsaturated polyester by solvent azeotropy | |
| CN103554381A (en) | Water-based acrylic acid modified saturated polyester resin and preparation method thereof | |
| JP2013521357A5 (en) | ||
| RU2012141623A (en) | WATER POLYURETHANE DISPERSIONS | |
| JP2016135870A (en) | Crosslinkable composition crosslinkable with latent base catalyst | |
| CN108329438B (en) | High-acid-resistance water-based epoxy dispersion and preparation method thereof | |
| CN105669962B (en) | A kind of preparation method of UV curing powder coating resin | |
| CN102358815A (en) | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method | |
| CN103030745B (en) | Water-based photo-cured unsaturated polyester and preparation method thereof | |
| CN107312134A (en) | A kind of dual cross-linking aqueous epoxy/polyacrylate hybridisation emulsion of room temperature and preparation method thereof | |
| CN107903800A (en) | A kind of water-based UV varnish of large arch dam and preparation method and application | |
| CN103951818A (en) | Sulphonic acid type water-based unsaturated polyester and application of sulphonic acid type water-based unsaturated polyester in coating | |
| CN105907290A (en) | Environment-friendly emulsion type water-based ultraviolet-curing plastic coating and preparation method thereof | |
| CN101864233B (en) | Novel water-based aluminum foil protective agent and preparation method | |
| CN104693371B (en) | Novel acrylic modified resin for aqueous two-component polyurethane coating | |
| CN104448268B (en) | Modified alkyd resin and preparation method thereof, two component light top coat top coats and preparation method thereof | |
| CN105949439A (en) | Preparation method of waterborne modified epoxy resin | |
| CN109081884A (en) | A kind of cross-linking modified high glaze water-based acrylic resin and preparation method thereof | |
| CN104479136A (en) | Nonionic epoxy emulsifier and preparation method thereof | |
| WO2024066428A1 (en) | Preparation method for solvent-free self-emulsifying water-soluble chlorinated polypropylene | |
| CN114686069B (en) | Polyacrylate resin modified waterborne epoxy emulsion and preparation method thereof | |
| CN104927000A (en) | Styrene-modified alkyd resin and preparation method thereof | |
| CN104371415B (en) | A kind of efficient paint remover and its preparation method | |
| CN104479080B (en) | A kind of water dispersible coatings prepared with pet waste and behenic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150506 Termination date: 20161207 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |