CN110092885A - A kind of UV curable urethane acrylate resin and preparation method thereof - Google Patents
A kind of UV curable urethane acrylate resin and preparation method thereof Download PDFInfo
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- CN110092885A CN110092885A CN201910446667.7A CN201910446667A CN110092885A CN 110092885 A CN110092885 A CN 110092885A CN 201910446667 A CN201910446667 A CN 201910446667A CN 110092885 A CN110092885 A CN 110092885A
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- diisocyanate
- curable urethane
- urethane acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of UV curable urethane acrylate resins and preparation method thereof, it include: to mix polyester diol, diisocyanate, catalyst, and it is stirred to react under the conditions of 65~75 DEG C, until isocyanide acid ion concentration reaches 50% of isocyanide acid ion initial concentration in the diisocyanate in reaction solution, to obtain the first reaction solution；Polymerization inhibitor and hydroxy acrylate are added into first reaction solution, and is reacted under the conditions of 65~75 DEG C, until UV curable urethane acrylate resin is made less than 0.05% in isocyanide acid ion concentration in reaction solution.The present invention not only has good adhesive force and surface hardness, but also has excellent flexibility and water resistance.
Description
Technical field
The present invention relates to UV (Ultravioletray, ultraviolet light) light-cured resin technical field more particularly to a kind of UV
Curable urethane acrylate resin and preparation method thereof.
Background technique
With the raising of people's health consciousness and environmental consciousness, requirement of the people to coating is higher and higher, this makes tradition
The application of coating has become increasingly limited, and modern coatings are just towards high-performance, high-effect, high-environmental and high-decoration
Develop etc. the multi-functional direction being integrated.
UV light-cured resin is a kind of photoresist that molecular weight is relatively low, and photocuring reaction can be carried out by having
Group (such as all kinds of unsaturated double-bonds), can be fully cured under ultraviolet light.In photocuring final products, UV photocuring
Resin is material of main part, its performance determines the main performance of photocuring final products substantially, thus UV light-cured resin without
It is suspected to be the important link of photocuring product design.
In UV light-cured resin, polyurethane acrylate resin has the characteristics that hardness is high, glossiness is good, toughness is strong,
Therefore polyurethane acrylate resin is the UV light-cured resin being most widely used.
In the prior art, flexible although polyurethane acrylate resin has good adhesive force and surface hardness
Property and water resistance are generally lower, especially applied in hard plastic, metal finishing ink, adhesive its flexibility and
Water resistance is worse, therefore is badly in need of the polyurethane acrylate resin that exploitation has excellent flexibility and water resistance.
Summary of the invention
For above-mentioned shortcoming in the prior art, the present invention provides a kind of UV curable urethane acrylate trees
Rouge and preparation method thereof not only has good adhesive force and surface hardness, but also has excellent flexibility and water resistance,
Can be widely applied to woodenware lacquer, hard plastic varnish, lithographic plate and the binder of silk-screen printing, metal finishing ink and coating,
The numerous areas such as electronics adhesive.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of UV curable urethane acrylate resin, comprising:
Step 1 mixes polyester diol, diisocyanate, catalyst, and stirs under the conditions of 65~75 DEG C
Reaction, until isocyanide acid ion concentration reaches 50% of isocyanide acid ion initial concentration in the diisocyanate in reaction solution,
To obtain the first reaction solution；
Polymerization inhibitor and hydroxy acrylate are added in step 2, the first reaction solution of Xiang Suoshu, and under the conditions of 65~75 DEG C into
Row reaction, until UV curable urethane acrylate resin is made less than 0.05% in isocyanide acid ion concentration in reaction solution.
Preferably, the ratio between polyester diol, diisocyanate, hydroxy acrylate, catalyst, mass parts of polymerization inhibitor
Are as follows: 40~50 parts of polyester diol, 35~45 parts of diisocyanate, 12~18 parts of hydroxy acrylate, catalyst 0.02~
0.10 part, 0.04~0.12 part of polymerization inhibitor.
Preferably, polyester diol, diisocyanate, hydroxy acrylate, catalyst, polymerization inhibitor water content be below
500ppm。
Preferably, the diisocyanate is isoflurane chalcone diisocyanate, diformazan group diisocyanate, dicyclohexyl first
Alkane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene diisocyanate, hexamethylene diisocyanate, hydrogenation phenyl
At least one of methane diisocyanate, hexamethylene diisocyanate.
Preferably, the hydroxy acrylate is hydroxyethyl methacrylate, methacrylate hydroxypropyl acrylate, acrylic acid hydroxyl
At least one of ethyl ester, hydroxypropyl acrylate.
Preferably, the catalyst is one of dibutyl tin dilaurate, organo-bismuth.
Preferably, polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, 2,5- dimethyl hydroquinones.
Preferably, the preparation method of the polyester diol includes: according to binary acid: dihydric alcohol: catalyst for esterification reaction:
The ratio between antioxidant=55~65:35~45:0.05~0.15:0.5~1.5 mass parts, dihydric alcohol, binary acid, esterification is anti-
It answers catalyst, antioxidant to mix, and carries out esterification at 230~240 DEG C, until acid value is less than 20mgKOH/g
When, terminate esterification；Then carry out polycondensation reaction, vacuum degree control in -0.065~-0.095MPa, the reaction time is 1~
3h, until acid value obtains polyester diol less than 1.0mgKOH/g and when hydroxyl value is 180~200mgKOH/g.
Preferably, the binary acid is at least one of adipic acid, succinic acid；The dihydric alcohol is new penta 2
At least one of alcohol, 1,4- butanediol, ethylene glycol；The catalyst for esterification reaction is tetra-n-butyl titanate, monobutyl oxygen
Change one of tin, stannous oxalate；The antioxidant is one of triphenyl phosphite, triphenylphosphine.
A kind of UV curable urethane acrylate resin, using above-mentioned UV curable urethane acrylate resin
Preparation method is prepared.
As seen from the above technical solution provided by the invention, UV light-cured polyurethane acrylic acid provided by the present invention
The preparation method of ester resin, with the polyester diol of special ratios, diisocyanate, catalyst, polymerization inhibitor and hydroxy acrylic acid
Ester is primary raw material, and is divided into two steps and is reacted, and is controlled by the reaction temperature to each step, and pass through
Isocyanide acid ion concentration in each step is detected to determine reaction time and the reaction end of each step, to finally prepare
The UV curable urethane acrylate resin that flexible waterproof is had excellent performance.The present invention is according to the different of reaction temperature and product
Cyanic acid ion concentration controls the production technology of resins synthesis, the UV light-cured polyurethane third that the flexible waterproof of synthesis is had excellent performance
Alkene acid ester resin not only has good adhesive force and surface hardness after film forming, but also has excellent toughness and water resistance
Can, it can be widely applied to woodenware lacquer, hard plastic varnish, lithographic plate and the binder of silk-screen printing, metal finishing ink and painting
The numerous areas such as material, electronics adhesive.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiment of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, belongs to protection scope of the present invention.
UV curable urethane acrylate resin provided by the present invention and preparation method thereof is retouched in detail below
It states.The content being not described in detail in the embodiment of the present invention belongs to the prior art well known to professional and technical personnel in the field.
A kind of UV curable urethane acrylate resin, preparation method may comprise steps of:
Step 1 mixes polyester diol, diisocyanate, catalyst, and stirs under the conditions of 65~75 DEG C
Reaction, until isocyanide acid ion concentration reaches 50% of isocyanide acid ion initial concentration in the diisocyanate in reaction solution,
To obtain the first reaction solution.
Polymerization inhibitor and hydroxy acrylate are added in step 2, the first reaction solution of Xiang Suoshu, and under the conditions of 65~75 DEG C into
Row reaction, until UV curable urethane acrylate resin is made less than 0.05% in isocyanide acid ion concentration in reaction solution.
Specifically, the preparation method of the UV curable urethane acrylate resin may include following embodiments:
(1) polyester diol, diisocyanate, hydroxy acrylate, catalyst, polymerization inhibitor water content be below
500ppm.The ratio between the polyester diol, diisocyanate, hydroxy acrylate, catalyst, mass parts of polymerization inhibitor are as follows: (40
~50): (35~45): (12~18): (0.02~0.10): (0.04~0.12).
(2) diisocyanate is isoflurane chalcone diisocyanate, diformazan group diisocyanate, dicyclohexyl methyl hydride two
Isocyanates, '-diphenylmethane diisocyanate, terephthalylidene diisocyanate, hexamethylene diisocyanate, hydrogenation phenylmethane
At least one of diisocyanate, hexamethylene diisocyanate.
(3) hydroxy acrylate is hydroxyethyl methacrylate, methacrylate hydroxypropyl acrylate, acrylic acid hydroxyl second
At least one of ester, hydroxypropyl acrylate.
(4) catalyst is one of dibutyl tin dilaurate, organo-bismuth.
(5) polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, 2,5- dimethyl hydroquinones.
(6) polyester diol is to pass through esterification and certain vacuum at a certain temperature by binary acid and dihydric alcohol
It spends obtained by lower polycondensation reaction；Its specific preparation method may include: according to binary acid: dihydric alcohol: catalyst for esterification reaction:
The ratio between antioxidant=55~65:35~45:0.05~0.15:0.5~1.5 mass parts, dihydric alcohol, binary acid, esterification is anti-
It answers catalyst, antioxidant to mix, and carries out esterification at 230~240 DEG C, until acid value is less than 20mgKOH/g
When, terminate esterification；Then carry out polycondensation reaction, vacuum degree control in -0.065~-0.095MPa, the reaction time is 1~
3h, until acid value obtains polyester diol less than 1.0mgKOH/g and when hydroxyl value is 180~200mgKOH/g.Wherein, described
Binary acid be at least one of adipic acid, succinic acid；The dihydric alcohol is neopentyl glycol, 1,4- butanediol, ethylene glycol
At least one of；The catalyst for esterification reaction is tetra-n-butyl titanate, Mono-n-butyltin, one in stannous oxalate
Kind；The antioxidant is one of triphenyl phosphite, triphenylphosphine.
Further, the preparation method of UV curable urethane acrylate resin provided by the present invention, with specific ratio
Polyester diol, diisocyanate, catalyst, polymerization inhibitor and the hydroxy acrylate of example are primary raw material, and are divided into two
Step is reacted, and is controlled by the reaction temperature to each step, and by detecting isocyanide acid ion in each step
Concentration determines reaction time and the reaction end of each step, to finally prepare the UV light that flexible waterproof is had excellent performance
Cured polyurethane acrylate resin.The present invention is that resin conjunction is controlled according to the isocyanic acid ion concentration of reaction temperature and product
At production technology, the UV curable urethane acrylate resin that the flexible waterproof of synthesis is had excellent performance not only has after film forming
There are good adhesive force and a surface hardness, and there is excellent toughness and water resistance, can be widely applied to woodenware lacquer, hard
Matter plastic cement varnish, lithographic plate and the numerous areas such as the binder of silk-screen printing, metal finishing ink and coating, electronics adhesive.
To sum up, the embodiment of the present invention not only has good adhesive force and a surface hardness, but also with excellent soft
Toughness and water resistance can be widely applied to binder, the metal of woodenware lacquer, hard plastic varnish, lithographic plate and silk-screen printing
The numerous areas such as decorative ink and coating, electronics adhesive.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
UV curable urethane acrylate resin provided by the present invention and preparation method thereof is described in detail in body embodiment.
Embodiment 1
A kind of UV curable urethane acrylate resin, preparation method may comprise steps of:
Step A1, according to adipic acid: 1,4- butanediol: tetra-n-butyl titanate: triphenyl phosphite=60:39:0.1:0.9
The ratio between mass parts, adipic acid, 1,4-butanediol, tetra-n-butyl titanate, triphenyl phosphite are mixed, and 240
Esterification is carried out at DEG C, until when acid value is less than 20mgKOH/g, reaction time 7h terminates esterification；Then polycondensation is carried out
Reaction, vacuum degree control is in -0.095MPa, reaction time 2h, until acid value is less than 1.0mgKOH/g and hydroxyl value is
When 185mgKOH/g, polyester diol is made.
Step A2, polyester diol, isoflurane chalcone diisocyanate, organo-bismuth are mixed, and in 70 DEG C of conditions
Under be stirred to react, until reaction solution in isocyanide acid ion concentration reach in the isoflurane chalcone diisocyanate at the beginning of isocyanide acid ion
The 50% of beginning concentration, recording reacting time 3.5h, to obtain the first reaction solution.
Step A3, p-hydroxyanisole and hydroxy-ethyl acrylate are added in the first reaction solution of Xiang Suoshu, and in 70 DEG C of conditions
Under reacted, until reaction solution in isocyanide acid ion concentration less than 0.05%, recording reacting time 4h, filtering and discharging, i.e.,
The UV curable urethane acrylate resin that obtained flexible waterproof is had excellent performance.
Wherein, polyester diol, isoflurane chalcone diisocyanate, hydroxy-ethyl acrylate, organo-bismuth, p-hydroxyanisole
The ratio between mass parts 45:40:14.8:0.1:0.1.
Embodiment 2
A kind of UV curable urethane acrylate resin, preparation method may comprise steps of:
Step B1, according to adipic acid: ethylene glycol: tetra-n-butyl titanate: triphenyl phosphite=64:35:0.1:0.9 matter
The ratio between part is measured, adipic acid, ethylene glycol, tetra-n-butyl titanate, triphenyl phosphite are mixed, and is carried out at 240 DEG C
Esterification, until when acid value is less than 20mgKOH/g, reaction time 7h terminates esterification；Then polycondensation reaction is carried out, very
Reciprocal of duty cycle control is in -0.095MPa, reaction time 2h, when acid value is less than 1.0mgKOH/g and hydroxyl value is 178mgKOH/g,
Polyester diol is made.
Step B2, polyester diol, hydrogenation methylenebis phenyl isocyanate, dibutyl tin dilaurate are blended in one
It rises, and is stirred to react under the conditions of 70 DEG C, until to reach the hydrogenation phenylmethane two different for isocyanide acid ion concentration in reaction solution
The 50% of isocyanide acid ion initial concentration, recording reacting time 4h in cyanate, to obtain the first reaction solution.
Step B3, p-hydroxyanisole and hydroxy-ethyl acrylate are added in the first reaction solution of Xiang Suoshu, and in 70 DEG C of conditions
Under reacted, until reaction solution in isocyanide acid ion concentration less than 0.05%, recording reacting time 4h, filtering and discharging, i.e.,
The UV curable urethane acrylate resin that obtained flexible waterproof is had excellent performance.
Wherein, polyester diol, hydrogenation methylenebis phenyl isocyanate, hydroxy-ethyl acrylate, dibutyl tin dilaurate,
The ratio between mass parts of hydroquinone 47:40:12.8:0.1:0.1.
Embodiment 3
A kind of UV curable urethane acrylate resin, preparation method may comprise steps of:
Step C1, according to adipic acid: neopentyl glycol: tetra-n-butyl titanate: triphenyl phosphite=58:41:0.1:0.9
The ratio between mass parts mix adipic acid, neopentyl glycol, tetra-n-butyl titanate, triphenyl phosphite, and at 240 DEG C
Esterification is carried out, until when acid value is less than 20mgKOH/g, reaction time 7h terminates esterification；Then it is anti-to carry out polycondensation
It answers, vacuum degree control is in -0.095MPa, reaction time 2h, until acid value is less than 1.0mgKOH/g and hydroxyl value is 178mgKOH/
When g, polyester diol is made.
Step C2, polyester diol, isoflurane chalcone diisocyanate, dibutyl tin dilaurate are mixed, and
It is stirred to react under the conditions of 75 DEG C, until isocyanide acid ion concentration reaches different in the isoflurane chalcone diisocyanate in reaction solution
The 50% of cyanic acid ion initial concentration, recording reacting time 4h, to obtain the first reaction solution.
Step C3, hydroquinone and hydroxyethyl methacrylate are added in the first reaction solution of Xiang Suoshu, and in 75 DEG C of conditions
Under reacted, until reaction solution in isocyanide acid ion concentration less than 0.05%, recording reacting time 4h, filtering and discharging, i.e.,
The UV curable urethane acrylate resin that obtained flexible waterproof is had excellent performance.
Wherein, polyester diol, isoflurane chalcone diisocyanate, hydroxyethyl methacrylate, dibutyl tin dilaurate,
The ratio between mass parts of p-hydroxyanisole 45:40:14.8:0.1:0.1.
Embodiment 4
A kind of UV curable urethane acrylate resin, preparation method may comprise steps of:
Step D1, according to adipic acid: 1,4- butanediol: tetra-n-butyl titanate: triphenyl phosphite=60:39:0.1:0.9
The ratio between mass parts, adipic acid, 1,4-butanediol, tetra-n-butyl titanate, triphenyl phosphite are mixed, and 240
Esterification is carried out at DEG C, until when acid value is less than 20mgKOH/g, reaction time 7h terminates esterification；Then polycondensation is carried out
Reaction, vacuum degree control is in -0.095MPa, reaction time 2h, until acid value is less than 1.0mgKOH/g and hydroxyl value is
When 185mgKOH/g, polyester diol is made.
Step D2, polyester diol, dicyclohexyl methyl hydride diisocyanate, organo-bismuth are mixed, and at 70 DEG C
Under the conditions of be stirred to react, until reaction solution in isocyanide acid ion concentration reach isocyanide in the dicyclohexyl methyl hydride diisocyanate
The 50% of acid ion initial concentration, recording reacting time 4h, to obtain the first reaction solution.
Step D3, p-hydroxyanisole and hydroxypropyl acrylate are added in the first reaction solution of Xiang Suoshu, and in 70 DEG C of conditions
Under reacted, until reaction solution in isocyanide acid ion concentration less than 0.05%, recording reacting time 4h, filtering and discharging, i.e.,
The UV curable urethane acrylate resin that obtained flexible waterproof is had excellent performance.
Wherein, polyester diol, dicyclohexyl methyl hydride diisocyanate, hydroxypropyl acrylate, organo-bismuth, para hydroxybenzene first
The ratio between mass parts of ether 48:37:14.8:0.1:0.1.
Embodiment 5
A kind of UV curable urethane acrylate resin, preparation method may comprise steps of:
Step E1, according to adipic acid: ethylene glycol: tetra-n-butyl titanate: triphenylphosphine=57:42:0.1:0.9 mass parts
The ratio between, adipic acid, ethylene glycol, tetra-n-butyl titanate, triphenylphosphine are mixed, and esterification is carried out at 240 DEG C,
Until when acid value is less than 20mgKOH/g, reaction time 7h terminates esterification；Then polycondensation reaction, vacuum degree control are carried out
In -0.095MPa, reaction time 2h, until polyester is made less than 1.0mgKOH/g and when hydroxyl value is 195mgKOH/g in acid value
Dihydric alcohol.
Step E2, polyester diol, isoflurane chalcone diisocyanate, organo-bismuth are mixed, and in 70 DEG C of conditions
Under be stirred to react, until reaction solution in isocyanide acid ion concentration reach in the isoflurane chalcone diisocyanate at the beginning of isocyanide acid ion
The 50% of beginning concentration, recording reacting time 3.5h, to obtain the first reaction solution.
Step E3, p-hydroxyanisole and hydroxy propyl methacrylate are added in the first reaction solution of Xiang Suoshu, and at 70 DEG C
Under the conditions of reacted, until reaction solution in isocyanide acid ion concentration less than 0.05%, recording reacting time 4h is filtered out
Material, obtains the UV curable urethane acrylate resin that flexible waterproof is had excellent performance.
Wherein, polyester diol, isoflurane chalcone diisocyanate, hydroxy propyl methacrylate, organo-bismuth, para hydroxybenzene first
The ratio between mass parts of ether 45:42:16.8:0.1:0.1.
Performance detection
The embodiment of the present invention 1~5 and UV curable urethane acrylate resin in the prior art are carried out following
The detection of toughness and water resistance:
(1) embodiment of the present invention 1~5 and UV in the prior art toughness: are tested using the method for cylinder curvature respectively
The toughness of curable urethane acrylate resin；UV curable urethane acrylate resin is prepared into coating coated in PC
On plate (polycarbonate plate), and the bending data in PC plate is tested, data are smaller, illustrate that toughness is better.
(2) water resistance: respectively by the embodiment of the present invention 1~5 and UV light-cured polyurethane propylene in the prior art
Acid ester resin is prepared into coating and is coated in PC plate, and is put into boiling 1h in 100 DEG C of water, and whether observation coating surface situation occurs
Variation.
Testing result is as shown in table 1 below:
Table 1
| Toughness | Water resistance performance | |
| Prior art products | 5mm | Whiten, blister |
| Embodiment 1 | 1mm | It is non-whitening, not blistering |
| Embodiment 2 | 1mm | It is non-whitening, not blistering |
| Embodiment 3 | 1mm | It is non-whitening, not blistering |
| Embodiment 4 | 1mm | It is non-whitening, not blistering |
| Embodiment 5 | 1mm | It is non-whitening, not blistering |
As above-mentioned table 1 it can be seen that UV curable urethane acrylate resin obtained by the embodiment of the present invention 1~5
With excellent toughness and water resistance, it is much better than UV curable urethane acrylate resin in the prior art.
To sum up, the embodiment of the present invention not only has good adhesive force and a surface hardness, but also with excellent soft
Toughness and water resistance can be widely applied to binder, the metal of woodenware lacquer, hard plastic varnish, lithographic plate and silk-screen printing
The numerous areas such as decorative ink and coating, electronics adhesive.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (10)
1. a kind of preparation method of UV curable urethane acrylate resin characterized by comprising
Step 1 mixes polyester diol, diisocyanate, catalyst, and stirs anti-under the conditions of 65~75 DEG C
It answers, until isocyanide acid ion concentration reaches 50% of isocyanide acid ion initial concentration in the diisocyanate in reaction solution, from
And obtain the first reaction solution；
Polymerization inhibitor and hydroxy acrylate are added in step 2, the first reaction solution of Xiang Suoshu, and is carried out anti-under the conditions of 65~75 DEG C
It answers, until UV curable urethane acrylate resin is made less than 0.05% in isocyanide acid ion concentration in reaction solution.
2. the preparation method of UV curable urethane acrylate resin according to claim 1, which is characterized in that polyester
The ratio between dihydric alcohol, diisocyanate, hydroxy acrylate, catalyst, mass parts of polymerization inhibitor are as follows:
3. the preparation method of UV curable urethane acrylate resin according to claim 1 or 2, which is characterized in that
Polyester diol, diisocyanate, hydroxy acrylate, catalyst, polymerization inhibitor water content be below 500ppm.
4. the preparation method of UV curable urethane acrylate resin according to claim 1 or 2, which is characterized in that
The diisocyanate is isoflurane chalcone diisocyanate, diformazan group diisocyanate, dicyclohexyl methyl hydride diisocyanate, two
Phenylmethane diisocyanate, terephthalylidene diisocyanate, hexamethylene diisocyanate, hydrogenation methylenebis phenyl isocyanate,
At least one of hexamethylene diisocyanate.
5. the preparation method of UV curable urethane acrylate resin according to claim 1 or 2, which is characterized in that
The hydroxy acrylate is hydroxyethyl methacrylate, methacrylate hydroxypropyl acrylate, hydroxy-ethyl acrylate, acrylic acid hydroxypropyl
At least one of ester.
6. the preparation method of UV curable urethane acrylate resin according to claim 1 or 2, which is characterized in that
The catalyst is one of dibutyl tin dilaurate, organo-bismuth.
7. the preparation method of UV curable urethane acrylate resin according to claim 1 or 2, which is characterized in that
The polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, 2,5- dimethyl hydroquinones.
8. the preparation method of UV curable urethane acrylate resin according to claim 1 or 2, which is characterized in that
The preparation method of the polyester diol includes: according to binary acid: dihydric alcohol: catalyst for esterification reaction: antioxidant=55~65:
The ratio between 35~45:0.05~0.15:0.5~1.5 mass parts, by dihydric alcohol, binary acid, catalyst for esterification reaction, antioxidant
It mixes, and carries out esterification at 230~240 DEG C, until terminating esterification when acid value is less than 20mgKOH/g；
Then polycondensation reaction is carried out, for vacuum degree control in -0.065~-0.095MPa, the reaction time is 1~3h, until acid value is less than
When 1.0mgKOH/g and hydroxyl value are 180~200mgKOH/g, polyester diol is obtained.
9. the preparation method of UV curable urethane acrylate resin according to claim 8, which is characterized in that described
Binary acid be at least one of adipic acid, succinic acid；The dihydric alcohol is neopentyl glycol, 1,4- butanediol, ethylene glycol
At least one of；The catalyst for esterification reaction is tetra-n-butyl titanate, Mono-n-butyltin, one in stannous oxalate
Kind；The antioxidant is one of triphenyl phosphite, triphenylphosphine.
10. a kind of UV curable urethane acrylate resin, which is characterized in that using any one of the claims 1 to 9
The preparation method of the UV curable urethane acrylate resin is prepared.
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| CN113736064A (en) * | 2021-09-29 | 2021-12-03 | 江苏睿浦树脂科技有限公司 | Water-emulsifiable UV (ultraviolet) photocuring anionic resin and preparation method thereof |
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