CN112876647A - Non-sticky polyurethane acrylate prepolymer, solid adhesive tape and preparation method thereof - Google Patents
Non-sticky polyurethane acrylate prepolymer, solid adhesive tape and preparation method thereof Download PDFInfo
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- CN112876647A CN112876647A CN202110148129.7A CN202110148129A CN112876647A CN 112876647 A CN112876647 A CN 112876647A CN 202110148129 A CN202110148129 A CN 202110148129A CN 112876647 A CN112876647 A CN 112876647A
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- 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
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- 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
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- 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
- C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a non-sticky polyurethane acrylate prepolymer, a solid adhesive sheet and a preparation method thereof. The non-sticky polyurethane acrylate prepolymer has the advantages of large molecular weight, environmental protection, no VOC (volatile organic compounds) emission, high UV curing speed, good toughness, small heat release and the like. The solid adhesive sheet for decorating and beautifying fingernails (toes) has the advantages of environmental protection, low smell, small heat release, simple and convenient molding and strong decorative effect by adding the photoinitiator, the auxiliary agent, the pigment and the like into the urethane acrylate prepolymer, and is suitable for manufacturing different types of models of beautiful nails.
Description
Technical Field
The invention relates to the field of nail-beautifying materials, and mainly relates to a non-sticky polyurethane acrylate prepolymer, a solid adhesive sheet and a preparation method thereof.
Background
Nail varnish, a cosmetic, is mainly used for decorating and beautifying the appearance of nails, and also has the functions of protecting and strengthening the nails which are particularly fragile in texture. Currently, nail polishes are largely divided into three categories, the first being oil-based, the second being UV nail polish, and the third being the two-year popular aqueous nail polish. The three nail polishes are mainly used by brushing, so that the nail extension is easy to brush when a consumer brushes the nail extension by himself, and the nail extension is easy to brush by the left hand and the right hand, so that the nail polish cannot be brushed smoothly and well. In addition, the used brushing or sizing tool is also eight-door, the steps are complicated, and the performance and the aesthetic degree of the nail polish are easily influenced due to the non-standard operation action. Therefore, consumers also expect a new nail polish variety that is easy to handle and more convenient to use. The UV nail polish gel, the extension gel and the carving gel are different types of gel types, cannot be universally used for one product, and need to be applied for three times. If one UV material completely meets the functional requirements of the nail polish glue, the extension glue and the carving glue, the material inventory and the product inventory of an enterprise can be greatly reduced, and the UV material not only can be convenient for a consumer to use, but also can reduce the inventory of the enterprise and improve the production efficiency and the enterprise profits.
The host resin for such UV materials is typically urethane acrylate. The resins currently on the market for extending glues (or carving glues) are conventional urethane acrylates, which on the one hand require the addition of large amounts of inert fillers to enhance the toughening and to reduce the surface tack of the glue, but with the problem that the glue becomes very viscous and poorly handleable, with limited increase in strength and toughness. On the other hand, a reactive diluent is required to be added to adjust the viscosity and the curing speed of the product, but the viscosity of the surface of the colloid is increased, the plasticity is reduced, and meanwhile, most of the reactive diluent is small molecular substances, so that the odor and the curing heat release are large, and the user feel is not friendly. I.e. traditional extension glues (or carving glues) all contain inert fillers and reactive diluents. Such as the extending glues of patents CN109528553A and CN108624220A and the carving glues of patents CN111265428A and CN106901997A, the formulations of which all contain reactive diluents and inert fillers, are conventional formulations, and the above mentioned problems cannot be avoided.
The urethane acrylate prepolymer is the most important component in the UV solid film and determines the basic properties of the material, such as curing speed, hardness, toughness, heat release and the like. Generally, the larger the molecular weight of the prepolymer, the slower the curing speed, the lower the hardness, the better the toughness, and the lower the exotherm; the smaller the molecular weight, the faster the curing speed, the higher the hardness, the poorer the toughness, and the higher the heat release, i.e., it is difficult to balance the molecular weight with the requirements of these four properties. The high molecular weight polyurethane acrylates described in patents CN101173032A and CN103833956A are synthesized from diols, diisocyanates and hydroxy acrylates, and the cured resins have good flexibility but low hardness and are not suitable for use in extending (or carving) glues.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a non-sticky urethane acrylate prepolymer, a solid-state adhesive sheet and a preparation method thereof, and aims to solve the problem that the curing speed, hardness, toughness and heat release of the urethane acrylate in the existing UV nail glue are difficult to be considered at the same time.
The technical scheme of the invention is as follows:
the non-sticky polyurethane acrylate prepolymer comprises the following raw materials in parts by weight:
100 parts of dihydric alcohol polymer, 50-105 parts of self-made dihydric alcohol, 45-100 parts of diisocyanate, 4-8 parts of active chain extender, 5-15 parts of blocking agent, 0.1-0.5 part of polymerization inhibitor and 0.1-0.5 part of organic tin catalyst.
The non-sticky polyurethane acrylate prepolymer is prepared by performing addition reaction on 100 parts by weight of alcohol amine compound and 180-460 parts by weight of isobornyl acrylate;
the alcohol amine compound is one or more than two of diethanol amine, 2-amino-2-methyl-1, 3-propylene glycol, 2-amino-1, 3-propylene glycol and 3-amino-1, 2-propylene glycol.
The non-sticky polyurethane acrylate prepolymer is characterized in that the dihydric alcohol polymer is polyether dihydric alcohol or polyester dihydric alcohol, and the relative molecular mass is 500-3000;
the diisocyanate is one or more than two of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and trimethyl-1, 6-hexamethylene diisocyanate;
the active chain extender is 2-methyl-2-acrylic acid-2, 3-dihydroxy propyl ester;
the end capping agent is one or more than two of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the polymerization inhibitor is one or more than two of p-hydroxyanisole, hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone;
the organic tin catalyst is one or more than two of dibutyltin dilaurate, stannous octoate, dibutyltin didodecyl sulfide, dibutyltin diacetate and dibutyltin dichloride.
The non-sticky polyurethane acrylate prepolymer is characterized in that the dihydric alcohol polymer is one or more than two of polytetrahydrofuran diol, polycaprolactone diol and polycarbonate diol; the molecular weight of the dihydric alcohol polymer is 1000-2000.
The non-sticky polyurethane acrylate prepolymer, wherein the molecular weight of the non-sticky polyurethane acrylate prepolymer is 5500 to 8500.
A method for preparing the non-sticky polyurethane acrylate prepolymer, which comprises the following steps:
A) dehydrating a dihydric alcohol polymer at high temperature in vacuum, cooling to 40-60 ℃, adding an organic tin catalyst, stirring uniformly, adding part of diisocyanate, reacting at 40-60 ℃ in a heat preservation way until the NCO value is 50 +/-1% of the initial value;
B) adding self-made dihydric alcohol, stirring, heating to 60-80 deg.C, reacting until NCO value is below 0.1%;
C) adding the rest diisocyanate, stirring uniformly, and carrying out heat preservation reaction at 60-80 ℃ until the NCO value is 50 +/-1% of the initial value in the step C;
D) adding an active chain extender and a polymerization inhibitor, stirring uniformly, reacting at 60-80 ℃ until the NCO value is 50 +/-1 percent of the initial NCO value in the step D, and cooling to 50-60 ℃;
E) adding an end-capping reagent, stirring uniformly, heating to 70-80 ℃, carrying out heat preservation reaction, and stopping the reaction until the NCO value is below 0.1%, thus obtaining a non-sticky polyurethane acrylic prepolymer; .
The preparation method of the non-sticky polyurethane acrylate prepolymer comprises the following steps of (1 +/-0.2) mixing partial diisocyanate with a diol polymer in a molar ratio of 2; the molar ratio of the self-made dihydric alcohol to the dihydric alcohol polymer is 2 (1 +/-0.2); the molar ratio of the rest diisocyanate to the dihydric alcohol polymer is 2 (1 +/-0.2); the molar ratio of the active chain extender to the dihydric alcohol polymer is (0.5 +/-0.1) to 1; the molar ratio of the end-capping reagent to the glycol polymer is (1-1.1): 1.
The preparation method of the non-sticky polyurethane acrylate prepolymer further comprises the following steps:
mixing an alcohol amine compound with an organic solvent, and dropwise adding isobornyl acrylate under the protection of nitrogen; wherein the molar ratio of the N-H bond to isobornyl acrylate in the alcohol amine compound is 1 (1-1.05);
controlling the dropping speed to keep the temperature of the materials below 20 ℃;
after the dropwise addition is finished, continuing the reaction at 10-30 ℃ until the content of C = C double bonds is below 0.1%;
the organic solvent was distilled off under reduced pressure to obtain a diol.
A solid adhesive sheet, wherein the solid adhesive sheet comprises the non-sticky polyurethane acrylic prepolymer.
The solid film comprises the following raw materials in parts by weight:
70-95 parts of non-sticky polyurethane acrylic prepolymer;
3-8 parts of a photoinitiator;
0.1-1 part of defoaming agent;
0.05-0.5 part of leveling agent;
0.05-0.1 part of polymerization inhibitor;
0-3 parts of adhesion promoter;
0-10 parts of pigment.
Has the advantages that: the non-sticky polyurethane acrylic prepolymer disclosed by the invention has the advantages of large molecular weight, environmental friendliness, no VOC (volatile organic compounds) emission, high UV (ultraviolet) curing speed, good toughness, small heat release and the like. The solid adhesive sheet for decorating and beautifying fingernails (toes) has the advantages of environmental protection, low smell, small heat release, simple and convenient molding and strong decorative effect by adding the photoinitiator, the auxiliary agent, the pigment and the like into the urethane acrylate prepolymer, and is suitable for manufacturing different types of models of beautiful nails.
Detailed Description
The invention provides a non-sticky polyurethane acrylate prepolymer, a solid film and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a non-sticky polyurethane acrylate prepolymer which comprises the following raw materials in parts by weight:
100 parts of dihydric alcohol polymer, 50-105 parts of self-made dihydric alcohol, 45-100 parts of diisocyanate, 4-8 parts of active chain extender, 5-15 parts of blocking agent, 0.1-0.5 part of polymerization inhibitor and 0.1-0.5 part of organic tin catalyst.
Wherein the dihydric alcohol polymer is polyether dihydric alcohol or polyester dihydric alcohol, and the relative molecular mass is 500-3000, preferably 1000-2000.
The dihydric alcohol polymer can be one or more than two of polytetrahydrofuran diol, polycaprolactone diol and polycarbonate diol.
The diisocyanate can be one or more than two of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and trimethyl-1, 6-hexamethylene diisocyanate.
The active chain extender may be 2-methyl-2-propenoic acid-2, 3-dihydroxypropyl ester.
The end-capping reagent may be one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The polymerization inhibitor can be one or more than two of p-hydroxyanisole, hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.
The organic tin catalyst can be one or more than two of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfur), dibutyltin diacetate and dibutyltin dichloride.
The self-prepared dihydric alcohol is prepared by performing addition reaction on 100 parts of alcohol amine compound and 180-460 parts of isobornyl acrylate according to parts by weight.
The alcohol amine compound is one or more than two of diethanol amine, 2-amino-2-methyl-1, 3-propylene glycol, 2-amino-1, 3-propylene glycol and 3-amino-1, 2-propylene glycol.
Preferably, the non-sticky urethane acrylate prepolymer has a molecular weight of 5500 to 8500.
The theoretical structural formula of the non-sticky polyurethane acrylate prepolymer is as follows:
r1 is the residual group of a diisocyanate after the loss of two isocyanate groups;
r2 is a residual group from the preparation of a diol after loss of the hydroxyl group;
r3 is a residual group of the dihydric alcohol polymer after losing hydroxyl;
r4 is a residual group of the active chain extender after hydroxyl is lost;
r5 is the residual group of the blocking agent after losing the hydroxyl group.
Further, R2 may be
、
、
、
One kind of (1).
The invention also provides a preparation method of the non-sticky polyurethane acrylate prepolymer, which comprises the following steps:
s1: synthesis of self-made diol:
mixing an alcohol amine compound with a proper amount of organic solvent, and dropwise adding isobornyl acrylate under the protection of nitrogen, wherein the molar ratio of N-H bonds in the alcohol amine compound to isobornyl acrylate is 1 (1-1.05); controlling the dropping speed to keep the temperature of the materials below 20 ℃; after the dropwise addition is finished, continuing the reaction at 10-30 ℃ until the content of C = C double bonds is below 0.1%; the organic solvent was distilled off under reduced pressure to obtain a diol.
Wherein the organic solvent can be one or more than two of toluene, xylene, dichloromethane, dichloroethane, dimethyl sulfoxide, cyclohexane and butanone; the amount of the organic solvent may be 2 to 3 times the amount of the alcohol amine compound.
S2: synthesis of non-sticky polyurethane acrylic prepolymer
A) Dehydrating a dihydric alcohol polymer at high temperature in vacuum, cooling to 40-60 ℃, adding an organic tin catalyst, stirring uniformly, adding part of diisocyanate, reacting at 40-60 ℃ in a heat preservation way until the NCO value is 50 +/-1% of the initial value; wherein the molar ratio of part of diisocyanate to the dihydric alcohol polymer is 2 (1 +/-0.2), and the high-temperature vacuum dehydration process is vacuum dehydration for 2 hours at 105 ℃;
B) adding the self-made dihydric alcohol, stirring uniformly, heating to 60-80 ℃, reacting until the NCO value is below 0.1%, wherein the molar ratio of the self-made dihydric alcohol to the dihydric alcohol polymer is 2 (1 +/-0.2);
C) adding the rest diisocyanate, stirring uniformly, and carrying out heat preservation reaction at 60-80 ℃ until the NCO value is 50 +/-1% of the initial value of the step C, wherein the molar ratio of the diisocyanate to the glycol polymer in the step C is 2 (1 +/-0.2);
D) adding an active chain extender and a polymerization inhibitor, stirring uniformly, reacting at 60-80 ℃ until the NCO value is 50 +/-1 percent of the initial NCO value of the step D, and cooling to 50-60 ℃, wherein the molar ratio of the active chain extender to the dihydric alcohol polymer is (0.5 +/-0.1): 1;
E) adding an end-capping agent, stirring uniformly, heating to 70-80 ℃, carrying out heat preservation reaction, and stopping the reaction until the NCO value is below 0.1%, thereby obtaining the non-sticky polyurethane acrylic prepolymer, wherein the molar ratio of the end-capping agent to the dihydric alcohol polymer is (1-1.1): 1.
Wherein, in S1, a morpholine addition method is adopted to determine the iodine value in the reaction system, so as to characterize the change of the content of C = C double bonds; in S2, the NCO group content in the system is monitored by a di-n-butylamine method, and the NCO group content is used for judging the degree of reaction.
The invention also provides a solid adhesive tape, which takes the non-sticky polyurethane acrylic prepolymer as main resin.
Further, the invention provides a preferable combination scheme of raw materials of the solid film, and the solid film comprises the following raw materials in parts by weight:
70-95 parts of non-sticky polyurethane acrylic prepolymer;
3-8 parts of a photoinitiator;
0.1-1 part of defoaming agent;
0.05-0.5 part of leveling agent;
0.05-0.1 part of polymerization inhibitor;
0-3 parts of adhesion promoter;
0-10 parts of pigment.
The photoinitiator, the defoamer, the leveling agent, the polymerization inhibitor, the adhesion promoter and the pigment are all commonly used raw materials in the field, and are not described herein. For example, the photoinitiator may be one or two or more selected from ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 1-hydroxycyclohexylphenylketone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, and the like. The defoaming agent may be polyoxypropylene polyoxyethylene glyceryl ether or others. The leveling agent can be one or more than two of polyether modified acrylic functional group dimethyl siloxane, BYK333 and the like. The polymerization inhibitor can be one or more than two of 2, 5-di-tert-butyl hydroquinone, methyl hydroquinone, phosphate modified acrylate and the like. The adhesion promoter may be KH560 or others.
Compared with the prior art, the invention has the following beneficial effects:
(1) the non-sticky polyurethane acrylate prepolymer provided by the invention contains a longer flexible chain segment in the main chain, and an acrylate photosensitive group is introduced into the side chain, so that the non-sticky polyurethane acrylate prepolymer has hardness and toughness, and is higher in UV curing speed and small in heat release.
(2) According to the invention, a carbon chain polycyclic structure is introduced into the side chain of the prepolymer through the self-made dihydric alcohol, so that the polarity of the molecular chain is reduced, and the interaction with hands is reduced, namely the prepolymer is not easy to stick to the hands.
(3) The non-sticky polyurethane acrylate prepolymer provided by the invention has the advantages of large molecular weight, difficulty in flowing and certain plasticity.
(4) According to the beneficial effects 1-3, the UV solid adhesive sheet for decorating and beautifying the fingernails and toenails, which is prepared by using the non-sticky polyurethane acrylate prepolymer, can achieve the effect of non-sticky hands without adding inert fillers, and does not need to add reactive diluents, so that the solid adhesive sheet has small smell and low heat release.
(5) The solid adhesive tape can also have the effect of non-sticky hands by adding the polyurethane acrylate prepolymer which is not sticky to hands, and can be directly kneaded and molded by hands or be made into different nail models by means of tools.
(6) The packaging mode which is more convenient to use can be selected, so that consumers can use the solid adhesive tape to decorate and beautify the nails more conveniently.
(7) The solid adhesive tape completely meets the functional requirements of nail polish glue, extension glue and carving glue, and realizes that one adhesive meets multiple effects of nail polish, extension glue and carving glue by different using methods.
The present invention is further illustrated by the following specific examples.
Example 1
S1: synthesis of self-made diols
According to the weight portion, 100 portions of 3-amino-1, 2-propylene glycol and 200 portions of dichloromethane are evenly mixed, nitrogen is introduced, 460 portions of isobornyl acrylate are started to be dripped, the dripping speed is controlled well during the period, and the temperature of the materials is kept below 20 ℃. After the addition was complete, the reaction was continued at 15 ℃ until the C = C double bond content was below 0.1%. The solvent was then distilled off under reduced pressure to obtain a glycol.
S2: synthesis of non-sticky polyurethane acrylic prepolymer
According to the weight portion, 100 portions of poly-tetramethyl ether glycol (Korean PTG2000, the relative molecular weight is 2000) are vacuumized for 2 hours at 105 ℃, the water content is removed, then the temperature is reduced to 40 ℃, 0.1 portion of dibutyltin dilaurate is added and stirred evenly, 26.5 portions of dicyclohexyl methane diisocyanate are added, the temperature is kept at 60 ℃ after the temperature is constant, and the reaction is carried out until the NCO value is 50 +/-1% of the initial value;
adding 51 parts of the self-made dihydric alcohol, heating to 80 ℃ for reaction, and reacting until the NCO value is below 0.1%;
then adding 22 parts of isophorone diisocyanate, and carrying out heat preservation reaction at 75 ℃ until the NCO value is 50 +/-1% of the initial value of the step;
adding 4 parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester and 0.3 part of 2-tert-butylhydroquinone, reacting at 68 ℃ until the NCO value is 50 +/-1 percent of the initial value of the step, and cooling to 50 ℃;
adding 7 parts of hydroxyethyl methacrylate, heating to 75 ℃, keeping the temperature, reacting until the NCO value is below 0.1%, and stopping the reaction to obtain the non-sticky polyurethane acrylic prepolymer with the predicted molecular weight of 8300.
Example 2
S1: synthesis of self-made diols
100 parts of 2-amino-1, 3-propanediol and 250 parts of dichloromethane are uniformly mixed according to parts by weight, nitrogen is introduced, 465 parts of isobornyl acrylate are added dropwise, the dropwise adding speed is controlled well during the period, and the temperature of the material is kept below 20 ℃. After the addition was complete, the reaction was continued at 10 ℃ until the C = C double bond content was below 0.1%. The solvent was then distilled off under reduced pressure to obtain a glycol.
S2: synthesis of non-sticky polyurethane acrylic prepolymer
According to the weight portion, 100 portions of polycarbonate dihydric alcohol (Asahi Kasei T4672, with the relative molecular weight of 2000) is vacuumized for 2 hours at 105 ℃, the water content is removed, then the temperature is reduced to 50 ℃, 0.1 portion of stannous octoate is added and stirred evenly, 17 portions of 1, 6-hexamethylene diisocyanate are added, the temperature is kept at 50 ℃ after the temperature is constant, and the reaction is carried out until the NCO value is 50 +/-1% of the initial value;
adding 51 parts of the self-made dihydric alcohol, heating to 70 ℃ for reaction, and reacting until the NCO value is below 0.1%;
then adding 23 parts of isophorone diisocyanate, and reacting at 70 ℃ in a heat preservation manner until the NCO value is 50 +/-1% of the initial value of the step;
adding 4 parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester and 0.15 part of p-hydroxyanisole, reacting at 70 ℃ until the NCO value is 50 +/-1% of the initial NCO value of the step, and cooling to 50 ℃;
adding 6 parts of hydroxyethyl methacrylate, heating to 75 ℃, keeping the temperature for reaction, and stopping the reaction until the NCO value is below 0.1 percent to obtain the non-sticky polyurethane acrylic prepolymer with the estimated molecular weight of 8000.
Example 3
S1: synthesis of self-made diols
100 parts of diethanolamine and 200 parts of dimethyl sulfoxide are uniformly mixed according to parts by weight, nitrogen is introduced, 200 parts of isobornyl acrylate is added dropwise, the dropwise adding speed is controlled well during the period, and the temperature of the material is kept below 20 ℃. After the addition was complete, the reaction was continued at 20 ℃ until the C = C double bond content was below 0.1%. The solvent was then distilled off under reduced pressure to obtain a glycol.
S2: synthesis of non-sticky polyurethane acrylic prepolymer
According to the weight portion, 100 portions of poly-tetramethyl ether glycol (Korean PTG1000, the relative molecular weight is 1000) are vacuumized for 2 hours at 105 ℃, the water content is removed, then the temperature is reduced to 50 ℃, 0.2 portion of dibutyltin diacetate is added and stirred evenly, 42 portions of trimethyl-1, 6-hexamethylene diisocyanate are added, the temperature is kept at 50 ℃ after the temperature is constant, the reaction is carried out until the NCO value is 50 +/-1 percent of the initial value;
adding 63 parts of the self-made dihydric alcohol, heating to 65 ℃ for reaction, and reacting until the NCO value is below 0.1%;
then 53 parts of dicyclohexyl methane diisocyanate is added, the reaction is carried out at the temperature of 75 ℃ until the NCO value is 50 +/-1% of the initial value of the step;
adding 8 parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester and 0.2 part of hydroquinone, reacting at 75 ℃ until the NCO value is 50 +/-1 percent of the initial NCO value of the step, and cooling to 60 ℃;
adding 15 parts of hydroxypropyl methacrylate, heating to 80 ℃, keeping the temperature, reacting until the NCO value is below 0.1%, and stopping the reaction to obtain the non-sticky polyurethane acrylic prepolymer with the molecular weight of 5500.
Example 4
S1: synthesis of self-made diols
According to the weight portion, 100 portions of 2-amino-1, 3-propanediol and 250 portions of dimethyl sulfoxide are evenly mixed, nitrogen is introduced, 460 portions of isobornyl acrylate are dripped, the dripping speed is controlled well during the period, and the temperature of the materials is kept below 20 ℃. After the addition was complete, the reaction was continued at 10 ℃ until the C = C double bond content was below 0.1%. The solvent was then distilled off under reduced pressure to obtain a glycol.
S2: synthesis of non-sticky polyurethane acrylic prepolymer
According to the weight portion, 100 portions of polycaprolactone diol (Paston Capa2125, the relative molecular weight is 1250) are vacuumized for 2 hours at 105 ℃, the water content is removed, then the temperature is reduced to 60 ℃, 0.3 portion of di (dodecyl sulfur) dibutyltin is added and stirred evenly, 28 portions of dicyclohexyl methane diisocyanate are added, the temperature is kept at 60 ℃ after the temperature is constant, the reaction is carried out until the NCO value is 50 +/-1% of the initial value;
adding 82 parts of the self-made dihydric alcohol, heating to 70 ℃ for reaction, and reacting until the NCO value is below 0.1%;
adding 27 parts of 1, 6-hexamethylene diisocyanate, and carrying out heat preservation reaction at 60 ℃ until the NCO value is 50 +/-1% of the initial value of the step;
adding 6.5 parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester and 0.3 part of p-hydroxyanisole, reacting at 60 ℃ until the NCO value is 50 +/-1% of the initial NCO value of the step, and cooling to 50 ℃;
adding 11 parts of hydroxypropyl acrylate, heating to 75 ℃, keeping the temperature, reacting until the NCO value is below 0.1%, and stopping the reaction to obtain the non-sticky polyurethane acrylic prepolymer with the molecular weight of 6600.
Example 5
S1: synthesis of self-made diols
100 parts by weight of 2-amino-2-methyl-1, 3-propanediol and 250 parts by weight of toluene are uniformly mixed, nitrogen is introduced, 400 parts of isobornyl acrylate is added dropwise, the dropwise adding speed is controlled, and the temperature of the materials is kept below 20 ℃. After the addition was complete, the reaction was continued at 30 ℃ until the C = C double bond content was below 0.1%. The solvent was then distilled off under reduced pressure to obtain a glycol.
S2: synthesis of non-sticky polyurethane acrylic prepolymer
According to the weight portion, 100 portions of polycaprolactone diol (Paston Capa2100, the relative molecular weight is 1000) are vacuumized for 2 hours at 105 ℃, the water is removed, then the temperature is reduced to 40 ℃, 0.2 portion of dibutyltin dilaurate is added and stirred evenly, 34.5 portions of 1, 6-hexamethylene diisocyanate are added, the temperature is kept at 40 ℃ after the temperature is constant, and the reaction is carried out until the NCO value is 50 +/-1% of the initial value;
adding 105 parts of the self-made dihydric alcohol, heating to 60 ℃ for reaction, and reacting until the NCO value is below 0.1%;
then adding 53 parts of dicyclohexyl methane diisocyanate, and reacting at the temperature of 80 ℃ until the NCO value is 50 +/-1% of the initial value of the step;
adding 8 parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester and 0.2 part of hydroquinone, reacting at 80 ℃ until the NCO value is 50 +/-1% of the initial value of the step, and cooling to 50 ℃;
adding 14 parts of hydroxyethyl acrylate, heating to 70 ℃, keeping the temperature, reacting until the NCO value is below 0.1%, and stopping the reaction to obtain the non-sticky polyurethane acrylic prepolymer, wherein the molecular weight is estimated to be 6200.
Example 6
S1: synthesis of self-made diols
100 parts by weight of 2-amino-2-methyl-1, 3-propanediol and 250 parts by weight of dichloromethane are uniformly mixed, nitrogen is introduced, 405 parts of isobornyl acrylate are added dropwise, the dropwise adding speed is controlled, and the temperature of the materials is kept below 20 ℃. After the addition was complete, the reaction was continued at 25 ℃ until the C = C double bond content was below 0.1%. The solvent was then distilled off under reduced pressure to obtain a glycol.
S2: synthesis of non-sticky polyurethane acrylic prepolymer
According to parts by weight, 100 parts of polycarbonate diol (Asahi Kasei T5651, the relative molecular weight is 1000) is vacuumized for 2 hours at 105 ℃, the water is removed, then the temperature is reduced to 40 ℃, 0.2 part of stannous octoate is added and stirred evenly, 34 parts of 1, 6-hexamethylene diisocyanate are added, the temperature is kept at 40 ℃ after the temperature is constant, and the reaction is carried out until the NCO value is 50 +/-1% of the initial value;
adding 105 parts of the self-made dihydric alcohol, heating to 60 ℃ for reaction, and reacting until the NCO value is below 0.1%;
then adding 45 parts of isophorone diisocyanate, and carrying out heat preservation reaction at 65 ℃ until the NCO value is 50 +/-1% of the initial value of the step;
adding 8 parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester and 0.2 part of 2, 5-di-tert-butylhydroquinone, reacting at 65 ℃ until the NCO value is 50 +/-1 percent of the initial value of the step, and cooling to 50 ℃;
adding 14.5 parts of hydroxypropyl acrylate, heating to 70 ℃, keeping the temperature, reacting until the NCO value is below 0.1%, and stopping the reaction to obtain the non-sticky polyurethane acrylic prepolymer with the molecular weight estimated to be 6000.
Comparative example 1 (without addition of reactive chain extender)
S1: synthesis of self-made diols
100 parts of 2-amino-1, 3-propanediol and 250 parts of dichloromethane are uniformly mixed according to parts by weight, nitrogen is introduced, 465 parts of isobornyl acrylate are added dropwise, the dropwise adding speed is controlled well during the period, and the temperature of the material is kept below 20 ℃. After the addition was complete, the reaction was continued at 10 ℃ until the C = C double bond content was below 0.1%. The solvent was then distilled off under reduced pressure to obtain a glycol.
S2: synthesis of polyurethane acrylic prepolymer
According to the weight portion, 100 portions of polycarbonate dihydric alcohol (Asahi Kasei T4672, with the relative molecular weight of 2000) is vacuumized for 2 hours at 105 ℃, the water content is removed, then the temperature is reduced to 50 ℃, 0.1 portion of stannous octoate is added and stirred evenly, 17 portions of 1, 6-hexamethylene diisocyanate are added, the temperature is kept at 50 ℃ after the temperature is constant, and the reaction is carried out until the NCO value is 50 +/-1% of the initial value;
adding 51 parts of the self-made dihydric alcohol, heating to 70 ℃ for reaction, and reacting until the NCO value is below 0.1%;
then adding 23 parts of isophorone diisocyanate, and reacting at 70 ℃ in a heat preservation manner until the NCO value is 50 +/-1% of the initial value of the step;
adding 1.6 parts of ethylene glycol, reacting at 70 ℃ until the NCO value is 50 +/-1% of the initial NCO value of the step, and cooling to 50 ℃;
adding 6 parts of hydroxyethyl methacrylate and 0.15 part of p-hydroxyanisole, heating to 75 ℃, keeping the temperature for reaction, and stopping the reaction until the NCO value is below 0.1 percent to obtain a polyurethane acrylic prepolymer, wherein the molecular weight is estimated to be 7800.
In this example, ethylene glycol was used in place of the reactive chain extender in order to keep the backbone length constant.
COMPARATIVE EXAMPLE 2 (No self-made dihydric alcohol)
According to the weight portion, 100 portions of polycarbonate dihydric alcohol (Asahi Kasei T4672, with the relative molecular weight of 2000) is vacuumized for 2 hours at 105 ℃, the water content is removed, then the temperature is reduced to 50 ℃, 0.1 portion of stannous octoate is added and stirred evenly, 17 portions of 1, 6-hexamethylene diisocyanate are added, the temperature is kept at 50 ℃ after the temperature is constant, and the reaction is carried out until the NCO value is 50 +/-1% of the initial value;
adding 7.6 parts of 1, 3-propylene glycol, heating to 70 ℃ for reaction, and reacting until the NCO value is below 0.1%;
then adding 23 parts of isophorone diisocyanate, and reacting at 70 ℃ in a heat preservation manner until the NCO value is 50 +/-1% of the initial value of the step;
adding 4 parts of 2-methyl-2-acrylic acid-2, 3-dihydroxypropyl ester and 0.15 part of p-hydroxyanisole, reacting at 70 ℃ until the NCO value is 50 +/-1% of the initial NCO value of the step, and cooling to 50 ℃;
adding 6 parts of hydroxyethyl methacrylate, heating to 75 ℃, keeping the temperature, reacting until the NCO value is below 0.1%, and stopping the reaction to obtain a polyurethane acrylic prepolymer, wherein the molecular weight is estimated to be 6200.
In this example, 1, 3-propanediol was used in place of the self-made diol in order to keep the backbone length constant.
100% of the prepolymer prepared in examples 1 to 6 and comparative examples 1 to 2 was added with 2% of photoinitiator 184 (CAS: 947-19-3) and heated, dissolved and stirred, and the related properties were measured, and the results are shown in Table 1.
TABLE 1 prepolymer Performance tables for examples 1-6 and comparative examples 1-2
| Surface tackiness of the gel | Curing energy (mJ/cm)2） | Hardness (Shao D) | Flexibility (mm) | Heat release amount | |
| Example 1 | Non-sticky hand | 850 | 75 | 1.5 | Ⅲ |
| Example 2 | Non-sticky hand | 700 | 80 | 1.5 | Ⅲ |
| Example 3 | Non-sticky hand | 700 | 80 | 4 | Ⅱ~Ⅲ |
| Example 4 | Non-sticky hand | 600 | 75 | 4 | Ⅲ |
| Example 5 | Non-sticky hand | 550 | 70 | 5 | Ⅲ |
| Example 6 | Non-sticky hand | 600 | 85 | 5 | Ⅱ~Ⅲ |
| Comparative example 1 | Non-sticky hand | 1200 | 55 | 0.5 | Ⅲ |
| Comparative example 2 | Sticky hand | 700 | 80 | 1.5 | Ⅱ~Ⅲ |
The properties in table 1 were measured as follows:
curing energy: electrodeless mercury lamp with light intensity of 20mW/cm2。
Hardness: electrodeless mercury lamp with light intensity of 20mW/cm2And curing for 3min by using a glue layer with the thickness of 2 mm.
Flexibility: GB/T1731-1993.
Heat release: the prepared glue is coated on the nail, and is irradiated by a 48W LED lamp for 60s, so that the heat release, the pain feeling I level, the pain-free heat feeling II level and the heat-free feeling III level in the UV process are sensed.
Comparing the test results of the above examples and comparative examples, it can be seen that the introduction of acrylate photosensitive groups into the side chains of the prepolymer can result in higher hardness and better toughness, as well as faster UV curing speed and less heat release. In addition, the effect of no sticking can be achieved by introducing a carbon chain polycyclic structure into the side chain of the prepolymer through self-made dihydric alcohol.
The photoinitiator, the auxiliary agent and the pigment shown in table 2 were added to the urethane acrylic prepolymer provided in example 2, and uniformly mixed to obtain a tack-free UV solid sticker sheet.
Preparing the non-sticky UV solid adhesive sheet, preheating the prepolymer at 70-90 ℃ for 30-60 minutes for later use, weighing all the materials in parts by weight, stirring the materials by a dispersion machine for 30-60 minutes, uniformly dispersing the materials, controlling the temperature at 70-90 ℃, vacuumizing, heating and discharging bubbles to obtain the non-sticky UV solid adhesive sheet.
The prepared product can be packaged in a conventional mode, can also be prepared into a sheet film for consumers to use, and can be used as nail polish glue, extension glue and carving glue.
TABLE 2 several proportions and Properties of UV solid-state adhesive sheet
| Ratio 1 | Ratio 2 | Ratio 3 | |
| Polyurethane acrylic prepolymer | 95 | 90 | 87.4 |
| 2,4, 6-Trimethylbenzoylphenylphosphonic acid ethyl ester | 2.6 | 4 | 4 |
| 1-hydroxycyclohexyl phenyl methanones | 2.6 | / | / |
| Phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide | / | 1 | 2 |
| Polyoxypropylene polyoxyethylene glyceryl ether | 0.1 | 0.25 | 0.5 |
| Polyether modified acrylic functional polydimethylsiloxane | 0.2 | / | / |
| BYK333 | / | 0.2 | / |
| 2, 5-di-tert-butylhydroquinone | 0.5 | / | / |
| Methyl-p-benzenediol | / | 0.05 | 0.1 |
| Phosphate ester-modified acrylic acid esters | / | 1.5 | / |
| KH560 | / | / | 2 |
| Black pulp with carbon black grinding fineness less than 30 micrometers | / | 2.7 | / |
| White pearl powder | / | 0.3 | / |
| White slurry with ground titanium dioxide fineness less than 20 mu m | / | / | 5 |
| Surface tackiness of the gel | Non-sticky hand | Non-sticky hand | Non-sticky hand |
| Operability of | Can be pasted with nail, prolonged and carved | Can be pasted with nail, prolonged and carved | Can be pasted with nail, prolonged and carved |
| Curing of 48w sun lamp | Good curing and proper hardness | Good curing and proper hardness | Good curing and proper hardness |
| Adhesion force | Meets the requirements | Meets the requirements | Meets the requirements |
In conclusion, the non-sticky polyurethane acrylic prepolymer has the advantages of large molecular weight, environmental protection, no VOC emission, high UV curing speed, good toughness, small heat release and the like. The solid adhesive sheet for decorating and beautifying fingernails (toes) has the advantages of environmental protection, low smell, small heat release, simple and convenient molding and strong decorative effect by adding the photoinitiator, the auxiliary agent, the pigment and the like into the urethane acrylate prepolymer, and is suitable for manufacturing different types of models of beautiful nails.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. The non-sticky polyurethane acrylate prepolymer is characterized by comprising the following raw materials in parts by weight:
100 parts of dihydric alcohol polymer, 50-105 parts of self-made dihydric alcohol, 45-100 parts of diisocyanate, 4-8 parts of active chain extender, 5-15 parts of blocking agent, 0.1-0.5 part of polymerization inhibitor and 0.1-0.5 part of organic tin catalyst.
2. The non-sticky polyurethane acrylate prepolymer according to claim 1, wherein the self-made diol is prepared by performing an addition reaction on 100 parts by weight of an alcohol amine compound and 180-460 parts by weight of isobornyl acrylate;
the alcohol amine compound is one or more than two of diethanol amine, 2-amino-2-methyl-1, 3-propylene glycol, 2-amino-1, 3-propylene glycol and 3-amino-1, 2-propylene glycol.
3. The non-sticky polyurethane acrylate prepolymer according to claim 1, wherein the diol polymer is polyether diol or polyester diol, and the relative molecular mass is 500-3000;
the diisocyanate is one or more than two of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and trimethyl-1, 6-hexamethylene diisocyanate;
the active chain extender is 2-methyl-2-acrylic acid-2, 3-dihydroxy propyl ester;
the end capping agent is one or more than two of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the polymerization inhibitor is one or more than two of p-hydroxyanisole, hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone;
the organic tin catalyst is one or more than two of dibutyltin dilaurate, stannous octoate, dibutyltin didodecyl sulfide, dibutyltin diacetate and dibutyltin dichloride.
4. The non-sticky polyurethane acrylate prepolymer according to claim 1 wherein the glycol polymer is one or more of polytetrahydrofuran diol, polycaprolactone diol, polycarbonate diol; the molecular weight of the dihydric alcohol polymer is 1000-2000.
5. The non-stick urethane acrylate prepolymer of claim 1 wherein the molecular weight of the non-stick urethane acrylate prepolymer is from 5500 to 8500.
6. A method for preparing the non-sticky polyurethane acrylate prepolymer as claimed in any one of claims 1 to 5, comprising the steps of:
A) dehydrating a dihydric alcohol polymer at high temperature in vacuum, cooling to 40-60 ℃, adding an organic tin catalyst, stirring uniformly, adding part of diisocyanate, reacting at 40-60 ℃ in a heat preservation way until the NCO value is 50 +/-1% of the initial value;
B) adding self-made dihydric alcohol, stirring, heating to 60-80 deg.C, reacting until NCO value is below 0.1%;
C) adding the rest diisocyanate, stirring uniformly, and carrying out heat preservation reaction at 60-80 ℃ until the NCO value is 50 +/-1% of the initial value in the step C;
D) adding an active chain extender and a polymerization inhibitor, stirring uniformly, reacting at 60-80 ℃ until the NCO value is 50 +/-1 percent of the initial NCO value in the step D, and cooling to 50-60 ℃;
E) adding an end-capping reagent, stirring uniformly, heating to 70-80 ℃, carrying out heat preservation reaction, and stopping the reaction until the NCO value is below 0.1%, thus obtaining a non-sticky polyurethane acrylic prepolymer; .
7. The method of preparing the non-sticky urethane acrylate prepolymer according to claim 6 wherein the molar ratio of the partial diisocyanate to the diol polymer is 2 (1 ± 0.2); the molar ratio of the self-made dihydric alcohol to the dihydric alcohol polymer is 2 (1 +/-0.2); the molar ratio of the rest diisocyanate to the dihydric alcohol polymer is 2 (1 +/-0.2); the molar ratio of the active chain extender to the dihydric alcohol polymer is (0.5 +/-0.1) to 1; the molar ratio of the end-capping reagent to the glycol polymer is (1-1.1): 1.
8. The method of preparing the non-sticky urethane acrylate prepolymer according to claim 6, further comprising the steps of:
mixing an alcohol amine compound with an organic solvent, and dropwise adding isobornyl acrylate under the protection of nitrogen; wherein the molar ratio of the N-H bond to isobornyl acrylate in the alcohol amine compound is 1 (1-1.05);
controlling the dropping speed to keep the temperature of the materials below 20 ℃;
after the dropwise addition is finished, continuing the reaction at 10-30 ℃ until the content of C = C double bonds is below 0.1%;
the organic solvent was distilled off under reduced pressure to obtain a diol.
9. A solid adhesive sheet, comprising the non-sticky polyurethane acrylic prepolymer according to any one of claims 1 to 5.
10. The solid sticker according to claim 9, wherein the solid sticker comprises the following raw materials in parts by weight:
70-95 parts of non-sticky polyurethane acrylic prepolymer;
3-8 parts of a photoinitiator;
0.1-1 part of defoaming agent;
0.05-0.5 part of leveling agent;
0.05-0.1 part of polymerization inhibitor;
0-3 parts of adhesion promoter;
0-10 parts of pigment.
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| CN113583211A (en) * | 2021-07-30 | 2021-11-02 | 浙江大学 | Polyurea acrylate oligomer and preparation method and application method thereof |
| CN114015014A (en) * | 2021-12-09 | 2022-02-08 | 南雄市沃太化工有限公司 | Elastic wiredrawing photocuring resin, preparation method thereof and elastic wiredrawing glue |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114015014A (en) * | 2021-12-09 | 2022-02-08 | 南雄市沃太化工有限公司 | Elastic wiredrawing photocuring resin, preparation method thereof and elastic wiredrawing glue |
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