CN112250831A - UV resin and preparation method thereof - Google Patents

UV resin and preparation method thereof Download PDF

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Publication number
CN112250831A
CN112250831A CN202011083798.2A CN202011083798A CN112250831A CN 112250831 A CN112250831 A CN 112250831A CN 202011083798 A CN202011083798 A CN 202011083798A CN 112250831 A CN112250831 A CN 112250831A
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monomer
formula
resin
reaction
polycarbonate diol
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CN112250831B (en
Inventor
徐涛
龙绪俭
鲁晓东
杨轩
熊东路
肖增钧
李斌仁
陈林生
许超平
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Shenzhen Feiyang Junyan New Material Co ltd
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Shenzhen Feiyang Xingye Technology Co ltd
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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Abstract

The invention relates to the technical field of coatings, and particularly relates to UV resin and a preparation method thereof. The UV resin is prepared from the following raw materials in parts by weight: (1) monomer A: the monomer A is one of a compound shown in a formula I and a compound shown in a formula II; (2) a monomer B: five-membered cyclic carbonates; (3) a monomer C: a diisocyanate; (4) a monomer D: the monomer D is one of a compound shown in a formula III and a compound shown in a formula IV; (5) a monomer E: a polycarbonate diol; (6) a solvent. The UV resin is aliphatic polycarbonate type polyurethane acrylate, has mechanical property adjustability and the characteristics of polyurethane and acrylate, and a cured film has good adhesive force and flexibility, is smooth in appearance and is full; the synthesis method is simple and is beneficial to realizing large-scale production.

Description

UV resin and preparation method thereof
Technical Field
The invention relates to the technical field of coatings, and particularly relates to UV resin and a preparation method thereof.
Background
The ultraviolet curing coating (UV coating) has the advantages of small environmental pollution, high curing speed, energy conservation, good performance of cured products, suitability for high-speed automatic production and the like. Due to the unique technology and application advantages of the UV coating, the UV coating is rapidly and widely applied to various industries and fields of electronic products, mechanical manufacturing, metal corrosion prevention and the like, and is known as a brand-new environment-friendly new material. The urethane acrylate is one of UV-curable resin oligomers, has the characteristics of both polyurethane and acrylate, and is mainly synthesized from polyol, polyisocyanate and hydroxyl-containing acrylate. Compared with the traditional polyurethane such as polyester polyurethane and polyether polyurethane, the aliphatic polycarbonate polyurethane has better water resistance, aging resistance and flexibility.
As UV-cured products evolve into the fields of plastics, metals, ceramics, glass, etc., some of the inherent drawbacks of UV coatings are increasingly manifested. Among them, the most important problem in the UV coating industry is the low mechanical properties of the coating after film formation, which is a bottleneck that prevents the UV coating from continuing to develop.
The five-membered ring carbonate is a cheap raw material, is mainly used in the battery industry, and is paid attention to the research work of taking the five-membered ring carbonate as a high polymer material synthetic raw material in order to expand the application range.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a UV resin, which is prepared from the following raw materials:
(1) monomer A: the monomer A is one of a compound shown in a formula I and a compound shown in a formula II;
Figure BDA0002719637370000011
wherein n and p are natural numbers;
(2) a monomer B: five-membered cyclic carbonates;
(3) a monomer C: a diisocyanate;
(4) a monomer D: the monomer D is one of a compound shown in a formula III and a compound shown in a formula IV;
Figure BDA0002719637370000021
(5) a monomer E: a polycarbonate diol;
(6) a solvent.
In a preferable technical scheme of the invention, in the compound shown in the formula I, n is 1-150; in the compound shown in the formula II, p is 1-30.
In a preferred embodiment of the present invention, in the compound represented by the formula III, R is2、R3Respectively selecting one of structures shown in formula V and formula VI;
Figure BDA0002719637370000022
as a preferable technical scheme of the invention, in the structure shown in the formula V, R5Is one of a structure shown in a formula VII and a structure shown in a formula VIII;
Figure BDA0002719637370000023
wherein m and t are natural numbers.
As a preferable technical scheme, in the structure shown in the formula VI, R6Is one of a structure shown in a formula IX and a structure shown in a formula X;
Figure BDA0002719637370000024
wherein r and q are natural numbers.
In a preferred embodiment of the present invention, the polycarbonate diol has a number average molecular weight of 500-3000.
The second aspect of the present invention provides a method for preparing the UV resin, comprising the steps of:
(1) mixing the monomer A, the monomer B and a solvent, reacting for 10-15h at 40-60 ℃, and removing the solvent to obtain an intermediate M;
(2) under the protection of inert gas, controlling the temperature to be 50-70 ℃, mixing the intermediate M with polycarbonate diol, adding the mixture into the monomer C, reacting for 3-6h, and cooling to obtain an intermediate N;
(3) and (3) under the protection of inert gas, controlling the temperature to be 50-70 ℃, adding the intermediate N into the monomer D, stopping the reaction when the-NCO value is 0, and cooling to obtain the compound.
In a preferred embodiment of the present invention, the molar ratio of the monomer a to the monomer B is 1: (1-5); the molar ratio of the intermediate M to the polycarbonate diol is 1: (1-15).
As a preferable technical scheme of the invention, the dosage of the monomer C is 1 to 5 times of the total molar quantity of the intermediate M and the polycarbonate diol; the molar ratio of the monomer C to the monomer D is 1: (1-5).
The third aspect of the invention provides the application of the UV resin, and the UV resin can be applied to the coating of plastic products, wooden products, metal products, ceramic products and glass products.
Advantageous effects
Compared with the prior art, the UV resin provided by the invention has the following advantages:
1. the UV resin is aliphatic polycarbonate urethane acrylate, has mechanical property adjustability, and can adjust and control the mechanical properties of a cured film, such as elongation at break, tensile strength and the like, by changing the molar ratio and the structure of an intermediate M and polycarbonate diol in raw materials for synthesizing the UV resin.
2. The UV resin has the characteristics of polyurethane and acrylate, and a cured film of the UV resin has good adhesive force and flexibility, is smooth in appearance and is full; the synthesis method is simple and is beneficial to realizing large-scale production.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above technical problems, a first aspect of the present invention provides a UV resin, which is prepared from the following raw materials:
(1) monomer A: the monomer A is one of a compound shown in a formula I and a compound shown in a formula II;
Figure BDA0002719637370000041
wherein n and p are natural numbers;
(2) a monomer B: five-membered cyclic carbonates;
(3) a monomer C: a diisocyanate;
(4) a monomer D: the monomer D is one of a compound shown in a formula III and a compound shown in a formula IV;
Figure BDA0002719637370000042
(5) a monomer E: a polycarbonate diol;
(6) a solvent.
Monomer A
In the invention, the monomer A is one of a compound shown in a formula I and a compound shown in a formula II;
Figure BDA0002719637370000043
wherein, n and p are natural numbers.
In a preferred embodiment, in the compounds of formula I, n is 1 to 150; in the compound shown in the formula II, p is 1-30.
In a preferred embodiment, in the compounds of formula I, R is1One selected from hydrogen and alkyl.
The alkyl group is not particularly limited, and methyl, ethyl and the like can be mentioned.
The inventor believes that in the compound of formula I, n is 1 to 150; in the compound shown in the formula II, p is 1-30; with the increase of the chain length of the monomer A, the mechanical property of the prepared UV resin after curing tends to be improved and then reduced, and when the chain length of the monomer A exceeds a certain length (n is more than 150 or p is more than 30), the mechanical property of the UV resin after curing is obviously reduced. The inventors considered that the reason is probably that the longer the chain length of the monomer A, the lower the content of hard segment units and the lower the mechanical properties.
Monomer B
In the invention, the monomer B is five-membered cyclic carbonate.
The five-membered cyclic carbonate is not particularly limited, and is commercially available and suitable for use in the present invention.
The inventor finds that the introduction of the cyclic carbonate enables the prepared intermediate M to contain beta hydroxyl and to easily react with isocyanate, on one hand, the cheap five-membered cyclic carbonate compound can obviously reduce the cost, on the other hand, the intermediate M generated by the reaction of amine and cyclic carbonate is matched with polycarbonate diol to synthesize the UV resin, the mechanical property of the UV resin is better than that of the traditional UV resin, and no auxiliary agent is needed in the reaction.
Monomer C
In the invention, the monomer C is diisocyanate.
The diisocyanate is not particularly limited, and is commercially available and suitable for use in the present invention.
In a preferred embodiment, mention may be made of the diisocyanates
Figure BDA0002719637370000051
Figure BDA0002719637370000052
Figure BDA0002719637370000053
And the like.
The inventors have found that only when a diisocyanate is used, the reaction is more controlled and an intermediate N blocked by-NCO groups is obtained, which further bridges structure D to form a UV resin; particularly, isophorone diisocyanate containing three methyl groups is adopted, the compatibility with the whole reaction system is good, and two-NCO groups with larger activity difference are beneficial to synthesis of a prepolymer.
Monomer D
In the invention, the monomer D is one of a compound shown in a formula III and a compound shown in a formula IV;
Figure BDA0002719637370000061
in a preferred embodiment, in the compound of formula III, R2、R3Respectively selecting one of structures shown in formula V and formula VI;
Figure BDA0002719637370000062
in the structure shown in the formula V, R is4Is one of hydrogen and alkyl.
The alkyl group is not particularly limited, and methyl, ethyl and the like can be mentioned.
In the structure shown in the formula V, R is5Is one of a structure shown in a formula VII and a structure shown in a formula VIII;
Figure BDA0002719637370000063
wherein m and t are natural numbers.
In a preferred embodiment, the structure of formula VII is shown wherein m is from 2 to 20.
In a preferred embodiment, in the structure of formula VIII, t is from 1 to 30.
In a preferred embodiment, in the structure of formula VIII, R7Is one of hydrogen and alkyl.
In the structure shown in the formula VI, R in the structure6Is one of a structure shown in a formula IX and a structure shown in a formula X;
Figure BDA0002719637370000064
wherein r and q are natural numbers.
In a preferred embodiment, in the structure of formula X, R8Is one of hydrogen and alkyl.
In the compound of formula IV, R is9Is hydrogen or alkyl; r10Is hydrogen or alkyl; r11Is hydrogen or alkyl.
Monomer E
In the present invention, the monomer E is a polycarbonate diol.
In a preferred embodiment, the polycarbonate diol has a number average molecular weight of 500-3000.
The inventors have found that the larger the number average molecular weight of the polycarbonate diol in the system, the lower the tensile strength after film formation of the resin obtained and the lower the hardness; the smaller the number average molecular weight of the polycarbonate diol, the lower the elongation at break after film formation of the resulting resin. The inventor unexpectedly finds that the comprehensive mechanical properties of the prepared resin are optimal only when polycarbonate diol with the molecular weight of 500-3000 is adopted, and particularly, after the polycarbonate diol is compounded with a compound shown as a formula I with n being 1-150 and an intermediate M prepared from five-membered cyclic carbonate, the resin forms a hard segment unit in a resin structure, so that the mechanical properties of the resin are remarkably improved.
Solvent(s)
In the present invention, the solvent is not particularly limited, and ethanol, methanol, acetone, methylene chloride and the like can be mentioned.
The second aspect of the present invention provides a method for preparing the UV resin, comprising the steps of:
(1) mixing the monomer A, the monomer B and a solvent, reacting for 10-15h at 40-60 ℃, and evaporating to remove the solvent to obtain an intermediate M;
(2) under the protection of inert gas, controlling the temperature to be 50-70 ℃, mixing the intermediate M with polycarbonate diol, adding the mixture into the monomer C, reacting for 3-6h, and cooling to obtain an intermediate N;
(3) and (3) under the protection of inert gas, controlling the temperature to be 50-70 ℃, adding the intermediate N into the monomer D, stopping the reaction when the-NCO value is 0, and cooling to obtain the compound.
In a preferred embodiment, the molar ratio of monomer a to monomer B is 1: (1-5); the molar ratio of the intermediate M to the polycarbonate diol is 1: (1-15).
The inventor finds in the experimental process that the dosage of the monomer C in the system cannot be lower than that of the intermediate M, and if the dosage of the monomer C is lower than that of the intermediate M, the intermediate M cannot completely react, the amount of the resin hard segment structure is reduced, and the mechanical property of the resin is reduced; in order to ensure the mechanical property of the resin, the dosage of the monomer C is not less than that of the intermediate M, and meanwhile, the excessive monomer C can also effectively inhibit the gelling phenomenon in the reaction process, so that the reaction can be carried out more smoothly.
In a preferred embodiment, the amount of the monomer C is 1 to 5 times the total molar amount of the intermediate M and the polycarbonate diol; the molar ratio of the monomer C to the monomer D is 1: (1-5).
The third aspect of the invention provides the application of the UV resin, and the UV resin can be applied to the coating of plastic products, wooden products, metal products, ceramic products and glass products.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a UV resin, and a method for preparing the UV resin, comprising the steps of:
(1) weighing 230g of polyetheramine D230 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, and stoppingReacting, cooling and removing the solvent to obtain an intermediate M1；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 14.5g of intermediate M is added1Mixing with 600g of polycarbonate diol (Mn 2000), slowly adding into 148g of isophorone diisocyanate for reaction, stopping the reaction when the-NCO value reaches the theoretical-NCO value (3.67 percent), and cooling to obtain an intermediate N1；
(3) Under the protection of inert gas, the temperature is controlled at 60 ℃, 571.8g of intermediate N is added1Slowly adding the mixture into 57.8g of hydroxyethyl acrylate for reaction, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
Example 2
Embodiment 2 provides a UV resin, and a method for preparing the UV resin, including the steps of:
(1) weighing 230g of polyetheramine D230 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, stopping the reaction, cooling, removing the solvent to obtain an intermediate M2；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 14.5g of intermediate M is added2And 333.3g of polycarbonate diol (Mn 2000) were slowly added to 148g of isophorone diisocyanate to react, and when the-NCO value reached the theoretical-NCO value (3.85%), the reaction was stopped, the temperature was reduced to obtain intermediate N2；
(3) Under the protection of inert gas, the temperature is controlled at 60 ℃, 327.5g of intermediate N is added2Slowly adding into 34.8g hydroxyethyl acrylate for reaction, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
Example 3
Embodiment 3 provides a method for preparing a UV resin, comprising the steps of:
(1) weighing 230g of polyetheramine D230 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, stopping the reaction, cooling, removing the solvent to obtain an intermediate M3；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 14.5g of intermediate M is added3And 200g of polycarbonate diol (Mn 2000) were mixed and 59.2g of iso-polycarbonate diol were slowly addedReacting in phorone diisocyanate, stopping the reaction when the-NCO value reaches the theoretical-NCO value (4.1 percent), and cooling to obtain an intermediate N3；
(3) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 205.2g of intermediate N is added3Slowly adding into 23.2g hydroxyethyl acrylate for reaction, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
Example 4
Embodiment 4 provides a method for preparing a UV resin, comprising the steps of:
(1) weighing 400g of polyetheramine D400 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, stopping the reaction, cooling, removing the solvent to obtain an intermediate M4；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 20.1g of intermediate M is added4Mixing with 600g of polycarbonate diol (Mn 2000), slowly adding into 148g of isophorone diisocyanate for reaction, stopping the reaction when the-NCO value reaches the theoretical-NCO value (3.64 percent), and cooling to obtain an intermediate N4；
(3) Under the protection of inert gas, the temperature is controlled at 60 ℃, 576.1g of intermediate N is added4Slowly adding the mixture into 57.8g of hydroxyethyl acrylate for reaction, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
Example 5
Embodiment 5 provides a method for preparing a UV resin, comprising the steps of:
(1) weighing 400g of polyetheramine D400 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, stopping the reaction, cooling, removing the solvent to obtain an intermediate M5；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 20.1g of intermediate M is added5And 333.3g of polycarbonate diol (Mn 2000) were slowly added to 88.8g of isophorone diisocyanate to react, and when the-NCO value reached the theoretical-NCO value (3.8%), the reaction was stopped, the temperature was reduced to obtain intermediate N5；
(3) Under the protection of inert gas, the temperature is controlled at 60 ℃, 331.7g of intermediate N is added5Slowly adding into 34.8g hydroxyethyl acrylate for reaction, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
Example 6
Embodiment 6 provides a method of preparing a UV resin, comprising the steps of:
(1) weighing 400g of polyetheramine D400 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, stopping the reaction, cooling, removing the solvent to obtain an intermediate M6；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 20.1g of intermediate M is added6Mixing with 200g of polycarbonate diol (Mn 2000), slowly adding 59.2g of isophorone diisocyanate for reaction, stopping the reaction when the-NCO value reaches the theoretical-NCO value (4 percent), and cooling to obtain an intermediate N6；
(3) Under the protection of inert gas, the temperature is controlled at 60 ℃, 209.5g of intermediate N is added6Slowly adding into 23.2g hydroxyethyl acrylate for reaction, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
Example 7
Embodiment 7 provides a method of preparing a UV resin, comprising the steps of:
(1) weighing 1000g of polyetheramine D2000, 200g of D400 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, stopping the reaction, cooling, removing the solvent to obtain an intermediate M7；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 46.8g of intermediate M is added7Mixing with 600g of polycarbonate diol (Mn 2000), slowly adding into 148g of isophorone diisocyanate for reaction, stopping the reaction when the-NCO value reaches the theoretical-NCO value (3.52 percent), and cooling to obtain an intermediate N7；
(3) 596.1g of intermediate N is added under the protection of inert gas and the temperature is controlled at 60 DEG7Slowly adding 52.3g of hydroxyethyl acrylate and 32.9g of ethanolamine modified acrylate to react, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
The synthesis method of the ethanolamine modified acrylate comprises the following steps: under the protection of dark place, adding 592.6g of trimethylolpropane triacrylate and 600.6g of tripropylene glycol diacrylate into a reaction bottle, heating to 50 ℃, slowly dripping 122g of ethanolamine for reaction, stopping the reaction after no raw material peak is detected by chromatography, and cooling to obtain the product.
Example 8
Embodiment 8 provides a method of preparing a UV resin, comprising the steps of:
(1) weighing 1000g of polyetheramine D2000, 200g of D400 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, stopping the reaction, cooling, removing the solvent to obtain an intermediate M8；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 46.8g of intermediate M is added8And 333.3g of polycarbonate diol (Mn 2000) were slowly added to 88.8g of isophorone diisocyanate to react, and when the-NCO value reached the theoretical-NCO value (3.58%), the reaction was stopped, the temperature was reduced to obtain intermediate N8；
(3) Under the protection of inert gas, temperature is controlled at 60 ℃, and 351.7g of intermediate N are added8Slowly adding 31.4g of hydroxyethyl acrylate and 19.7g of ethanolamine modified acrylate to react, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
The synthesis method of the ethanolamine modified acrylate comprises the following steps: under the protection of dark place, adding 592.6g of trimethylolpropane triacrylate and 600.6g of tripropylene glycol diacrylate into a reaction bottle, heating to 50 ℃, slowly dripping 122g of ethanolamine for reaction, stopping the reaction after no raw material peak is detected by chromatography, and cooling to obtain the product.
Example 9
Embodiment 9 provides a method of preparing a UV resin, comprising the steps of:
(1) weighing 1000g of polyetheramine D2000, 200g of D400 and 204g of propylene carbonate, adding the materials into a reaction bottle, heating to 50 ℃, reacting for 10 hours, stopping the reaction, cooling, removing the solvent to obtain an intermediate M9；
(2) Under the protection of inert gas, the temperature is controlled at 60 ℃, and 46.8g of intermediate M is added9Mixing with 200g of polycarbonate diol (Mn 2000), slowly adding 59.2g of isophorone diisocyanate for reaction, stopping the reaction when the-NCO value reaches the theoretical-NCO value (3.66 percent), and cooling to obtain an intermediate N9；
(3) Under the protection of inert gas, the temperature is controlled at 60 ℃, 229.5g of intermediate N is added9Slowly adding 20.9g of hydroxyethyl acrylate and 13.2g of ethanolamine modified acrylate to react, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
The synthesis method of the ethanolamine modified acrylate comprises the following steps: under the protection of dark place, adding 592.6g of trimethylolpropane triacrylate and 600.6g of tripropylene glycol diacrylate into a reaction bottle, heating to 50 ℃, slowly dripping 122g of ethanolamine for reaction, stopping the reaction after no raw material peak is detected by chromatography, and cooling to obtain the product.
Example 10
Embodiment 10 provides a method of preparing a UV resin, comprising the steps of:
(1) under the protection of inert gas, controlling the temperature at 60 ℃, slowly adding 200g of polycarbonate diol (Mn ═ 2000) into 44.4g of isophorone diisocyanate for reaction, stopping the reaction until the-NCO value reaches the theoretical-NCO value (3.43 percent), and cooling to obtain an intermediate 1;
(2) and (3) under the protection of inert gas, controlling the temperature to be 60 ℃, slowly adding 100g of the intermediate 1 into 9.5g of hydroxyethyl acrylate for reaction, stopping the reaction when the-NCO value is 0, and cooling to obtain the compound.
Example 11
Embodiment 11 provides a method of preparing a UV resin, comprising the steps of:
(1) under the protection of inert gas, controlling the temperature at 60 ℃, slowly adding 200g of polycarbonate diol (Mn ═ 2000) into 44.4g of isophorone diisocyanate for reaction, stopping the reaction until the-NCO value reaches the theoretical-NCO value (3.43 percent), and cooling to obtain an intermediate 2;
(2) and (3) under the protection of inert gas, controlling the temperature to be 60 ℃, slowly adding 122.2g of the intermediate 2 into 10.5g of hydroxyethyl acrylate and 6.6g of ethanolamine modified acrylate for reaction, stopping the reaction when the-NCO value is 0, and cooling to obtain the product.
In the above embodiments, the polyetheramines D230, D400, and D2000 are all purchased from south china stephani technologies ltd; isophorone diisocyanate was purchased from the german winning industry group; polycarbonate diol purchased from Asahi chemical Co., Ltd; ethanolamine and hydroxyethyl acrylate were purchased from Shanghai Aladdin Biotechnology Ltd; trimethylolpropane triacrylate and tripropylene glycol diacrylate are purchased from Yangxing specialty materials, Inc.
Performance testing
Weighing the UV resin prepared in the embodiment respectively, adding 2 wt% of initiator, 15 wt% of butyl acetate and 15 wt% of reactive diluent, stirring uniformly, then respectively coating on PC-ABS plates, placing in a 60 ℃ oven for drying to constant weight, taking out, cooling, and curing by a UV machine, wherein the coating thickness is 15 +/-2 microns.
And (3) performing performance characterization on the cured coating film:
1. adhesion force: testing according to the national standard GB/T9286;
2. hardness: testing according to the national standard GB/T6739;
3. flexibility: testing according to the national standard GB/T1731;
4. tensile properties (elongation at break and tensile strength): tested according to the national standard GB/T1040.1-2006.
The test results are shown in table 1.
TABLE 1 Performance test results of UV resins prepared in examples
Figure BDA0002719637370000121
Figure BDA0002719637370000131
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (10)

1. The UV resin is characterized in that raw materials for preparing the UV resin comprise the following components:
(1) monomer A: the monomer A is one of a compound shown in a formula I and a compound shown in a formula II;
Figure FDA0002719637360000011
wherein n and p are natural numbers;
(2) a monomer B: five-membered cyclic carbonates;
(3) a monomer C: a diisocyanate;
(4) a monomer D: the monomer D is one of a compound shown in a formula III and a compound shown in a formula IV;
Figure FDA0002719637360000012
(5) a monomer E: a polycarbonate diol;
(6) a solvent.
2. The UV resin of claim 1, wherein in the compound of formula I, n is 1 to 150; in the compound shown in the formula II, p is 1-30.
3. The UV resin according to claim 1, wherein in the compound represented by the formula III, R is2、R3Respectively selecting one of structures shown in formula V and formula VI;
Figure FDA0002719637360000013
4. the UV resin of claim 3, wherein R in the structure of formula V is5Is one of a structure shown in a formula VII and a structure shown in a formula VIII;
Figure FDA0002719637360000014
wherein m and t are natural numbers.
5. The UV resin of claim 3, wherein R in the structure of formula VI6Is one of a structure shown in a formula IX and a structure shown in a formula X;
Figure FDA0002719637360000021
wherein r and q are natural numbers.
6. The UV resin according to claim 1, wherein the polycarbonate diol has a number average molecular weight of 500-3000.
7. A method for preparing the UV resin according to any one of claims 1 to 6, comprising the steps of:
(1) mixing the monomer A, the monomer B and a solvent, reacting for 10-15h at 40-60 ℃, and removing the solvent to obtain an intermediate M;
(2) under the protection of inert gas, controlling the temperature to be 50-70 ℃, mixing the intermediate M with polycarbonate diol, adding the mixture into the monomer C, reacting for 3-6h, and cooling to obtain an intermediate N;
(3) and (3) under the protection of inert gas, controlling the temperature to be 50-70 ℃, adding the intermediate N into the monomer D, stopping the reaction when the-NCO value is 0, and cooling to obtain the compound.
8. The method for preparing the UV resin according to claim 7, wherein the molar ratio of the monomer A to the monomer B is 1: (1-5); the molar ratio of the intermediate M to the polycarbonate diol is 1: (1-15).
9. The method for preparing UV resin according to claim 7, wherein the amount of the monomer C is 1 to 5 times the total molar amount of the intermediate M and the polycarbonate diol; the molar ratio of the monomer C to the monomer D is 1: (1-5).
10. Use of a UV resin according to any of claims 1-6 for finishing of plastic, wood, metal, ceramic, glass products.
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