CN113736420A - Polyurethane type UV (ultraviolet) viscosity-reducing adhesive and preparation method thereof - Google Patents

Polyurethane type UV (ultraviolet) viscosity-reducing adhesive and preparation method thereof Download PDF

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CN113736420A
CN113736420A CN202111038398.4A CN202111038398A CN113736420A CN 113736420 A CN113736420 A CN 113736420A CN 202111038398 A CN202111038398 A CN 202111038398A CN 113736420 A CN113736420 A CN 113736420A
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hydroxyl
itaconic acid
terminated
aliphatic diol
viscose
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CN113736420B (en
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周正发
李盟
冯才兴
任凤梅
马海红
徐卫兵
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/68—Unsaturated polyesters

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Abstract

The invention provides a polyurethane type UV visbreaking adhesive and a preparation method thereof. According to the invention, hydroxyl-terminated itaconic acid-aliphatic diol copolyester is introduced into the UV viscose reducer, itaconic acid molecules contain two carboxyl groups and one double bond, the double bond on the side chain and the carboxyl group form a conjugated relation, the reaction activity is very high, the double bond generates a crosslinking reaction under UV irradiation, the 180-degree peel strength of the viscose reducer is reduced to 0.4N/25mm, the viscose reducer has an obvious visbreaking effect, and no residual gum or degumming exists.

Description

Polyurethane type UV (ultraviolet) viscosity-reducing adhesive and preparation method thereof
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a polyurethane type UV (ultraviolet) anti-adhesive and a preparation method thereof.
Background
With the trend of smart wearable products towards light, multifunctional, low power consumption and long endurance development of consumer electronic products such as mobile phones, the development of wafer level chip packaging is developing towards three directions of large size, multi-chip stacking and ultra-thin. However, as the wafer becomes thinner and thinner, the wafer becomes larger in size, and the wafer is very likely to be broken during the processing. Therefore, there is a need for an adhesive that bonds a wafer to a substrate, allows the wafer to complete the processing process, and allows the wafer to be easily separated from the substrate after the processing is completed.
The UV visbreaking adhesive is a novel adhesive material, has ultrahigh adhesive force, can ensure that an adhered object keeps stable, does not fall off or overlap in the processing process, and plays a role in protecting an unprocessed part. After the processing is finished, the adhesive force of the adhesive material can be instantly reduced through ultraviolet radiation, and the adhesive material can be easily taken down from the adhered material on the premise of not influencing the performance of the processed object.
The existing viscose reducing glue usually takes acrylic ester as a main body and is compounded with a polyfunctional monomer and a photoinitiator. However, the adhesive strength before UV curing is not ideal and the residual adhesive after UV curing is more.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the present invention aims to provide a polyurethane type UV visbreaking adhesive and a preparation method thereof, wherein hydroxyl-terminated itaconic acid-aliphatic diol copolyester is introduced to improve the visbreaking effect and the problem of adhesive residue of the UV visbreaking adhesive.
In order to achieve the above and other objects, the present invention provides a polyurethane type UV adhesive reducing agent, having the following structural formula:
Figure BDA0003248231990000011
wherein R is1Is composed of
Figure BDA0003248231990000021
R is CnH2n，n＝3-5；
R2Is composed of
Figure BDA0003248231990000022
One kind of (1).
In addition, the invention also provides a preparation method of the polyurethane type UV viscose reducer, which comprises the following steps:
s1 itaconic acid and alpha, omega-hydroxyl-terminated aliphatic diol are synthesized into hydroxyl-terminated itaconic acid-aliphatic diol copolyester with a side chain containing double bonds;
the S2 hydroxyl-terminated itaconic acid-aliphatic diol copolyester reacts with diisocyanate to prepare polyurethane type adhesive, and then photoinitiator is added to obtain the polyurethane type UV viscose reducer.
Preferably, step S1 includes:
adding a catalyst A into itaconic acid and an alpha, omega-hydroxyl-terminated aliphatic diol monomer, introducing nitrogen, reacting at 150-190 ℃ for 3-5 h, adding hydroquinone, and continuing to react for 5-7 h to obtain a reaction product;
dissolving the reaction product in N, N-dimethylformamide, and then adding xylene for precipitation to obtain hydroxyl-terminated itaconic acid-aliphatic diol copolyester;
the catalyst A is one or more of p-toluenesulfonic acid, tetrabutyl titanate and strong-acid styrene cation exchange resin.
Preferably, in step S1, the molar ratio of the α, ω -hydroxyl terminated aliphatic diol to the itaconic acid is 1.15 to 1.25: 1.
Preferably, in step S1, during the reaction of itaconic acid and alpha, omega-hydroxyl-terminated aliphatic diol monomer, the pressure of the reaction system is gradually reduced, and the temperature of the reaction system is gradually increased.
Preferably, the hydroxyl value of the hydroxyl-terminated itaconic acid-aliphatic diol copolyester is 60-130mgKOH/g, and the molecular weight is 800-3000.
Preferably, step S2 includes:
dissolving hydroxyl-terminated itaconic acid-aliphatic diol copolyester in a solvent A, adding a catalyst B, introducing nitrogen for protection, then dripping diisocyanate, and reacting for 4-7 hours at the temperature of 60-80 ℃;
adding a photoinitiator after the reaction is finished and uniformly stirring to obtain the polyurethane type UV reduced adhesive;
the solvent A is one or more of ethyl acetate, acetone and tetrahydrofuran;
the catalyst B is one or more of dibutyltin dilaurate, stannous octoate, triethylene diamine and triethanolamine.
Preferably, the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the hydroxyl-terminated itaconic acid-aliphatic diol copolyester is 1.1-1.5: 1.
Preferably, the diisocyanate is one or more of isophorone diisocyanate and toluene diisocyanate.
Preferably, the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methyl phenyl propane-1-ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-ketone and benzophenone.
As described above, the polyurethane-type UV visbreaker of the present invention has the following advantageous effects:
firstly, hydroxyl-terminated itaconic acid-aliphatic diol copolyester is introduced into the viscose reducing agent, itaconic acid molecules contain two carboxyl groups and a double bond, the double bond on a side chain and the carboxyl groups form a conjugated relation, the reaction activity is high, the double bond is subjected to a crosslinking reaction under UV irradiation, the 180-degree peel strength of the viscose reducing agent is reduced to 0.4N/25mm, and the viscose reducing effect is improved.
And secondly, the hydroxyl-terminated itaconic acid-aliphatic diol copolyester has a certain molecular weight, so that the toughness of a glue layer of the viscose reducer can be improved, and the viscose reducer cannot generate residual glue degumming after being subjected to UV irradiation and viscosity loss.
Thirdly, in the polyurethane type UV viscose reducer, a trifunctional monomer is not introduced, the components are simple, the reaction can be completed within 1-3 min, the reaction rate is high, and the conversion rate is high.
And because a multifunctional monomer is not required to be added, the peeling strength of the viscosity reducing adhesive before ultraviolet irradiation is not influenced, and the peeling strength of the viscosity reducing adhesive at 180 degrees before ultraviolet irradiation can reach 18N/25 mm.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all 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 and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
Note that "%" and "part(s)" shown in the description herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
The invention provides a preparation method of a polyurethane type UV (ultraviolet) viscose reducing agent, which comprises the following steps:
s1 itaconic acid and alpha, omega-hydroxyl-terminated aliphatic diol are synthesized into hydroxyl-terminated itaconic acid-aliphatic diol copolyester with a side chain containing double bonds;
the S2 hydroxyl-terminated itaconic acid-aliphatic diol copolyester reacts with diisocyanate to prepare polyurethane type adhesive, and then photoinitiator is added to obtain the polyurethane type UV viscose reducer.
Wherein, the hydroxyl-terminated itaconic acid-aliphatic diol copolyester prepared in the step S1 has the following chemical structural formula:
Figure BDA0003248231990000041
r is CnH2n，n＝3-5。
The polyurethane type UV visbreaking adhesive prepared in the step S2 has the following chemical structural formula:
Figure BDA0003248231990000042
R1is composed of
Figure BDA0003248231990000043
R2Is composed of
Figure BDA0003248231990000044
At least one of (1).
The itaconic acid molecule contains two carboxyl groups and a double bond, the double bond on the side chain and the carboxyl group form a conjugated relation, and the itaconic acid has high reaction activity. Therefore, itaconic acid and alpha, omega-hydroxyl-terminated aliphatic diol are utilized to synthesize hydroxyl-terminated itaconic acid-aliphatic diol copolyester with a double bond on a side chain, and then the hydroxyl-terminated itaconic acid-aliphatic diol copolyester with the double bond on the side chain is utilized to react with diisocyanate to prepare the polyurethane type UV visbreaking adhesive, wherein under UV irradiation, the double bond is subjected to a crosslinking reaction, so that the 180-degree peel strength of the visbreaking adhesive is reduced to 0.4N/25mm, and the visbreaking effect is obviously improved.
In an embodiment, step S1 specifically includes, for example:
s11, adding a catalyst A into itaconic acid and an alpha, omega-hydroxyl-terminated aliphatic diol monomer, introducing nitrogen, reacting at 150-190 ℃ for 3-5 h, adding hydroquinone, and continuing to react for 5-7 h to obtain a reaction product;
s12, dissolving the reaction product in N, N-dimethylformamide, and then adding xylene for precipitation to obtain the hydroxyl-terminated itaconic acid-aliphatic diol copolyester.
The catalyst a in step S1 can be, for example, one or more of p-toluenesulfonic acid, tetrabutyl titanate, and a strongly acidic styrene cation exchange resin, such as p-toluenesulfonic acid, a mixture of p-toluenesulfonic acid and tetrabutyl titanate, a strongly acidic styrene cation exchange resin, and the like. The amount of the catalyst A may be, for example, 0.5 to 1.5 parts by mass, for example, 0.5 part by mass per 1 part by mass per 1.5 parts by mass of the catalyst A, based on 100 parts by mass of itaconic acid.
In an embodiment, step S2 specifically includes, for example:
s21, dissolving hydroxyl-terminated itaconic acid-aliphatic diol copolyester in a solvent A, adding a catalyst B, introducing nitrogen for protection, dropwise adding diisocyanate into a reaction container, and reacting at 60-80 ℃ for 4-7 hours;
s22, adding a photoinitiator after the reaction is finished, and uniformly stirring to obtain the polyurethane type UV viscose reducer;
the solvent a in step S21 may be, for example, one or more of ethyl acetate, acetone, and tetrahydrofuran, such as ethyl acetate, acetone, or a mixture of ethyl acetate and tetrahydrofuran, etc. The amount of the solvent a may be, for example, 300 to 500 parts by mass, for example, 300 parts by mass per 400 parts by mass per 500 parts by mass of the solvent a, based on 100 parts by mass of the hydroxyl-terminated itaconic acid-aliphatic diol copolyester.
The catalyst B in step S22 can be, for example, one or more of dibutyltin dilaurate, stannous octoate, triethylenediamine, triethanolamine, such as dibutyltin dilaurate, for example, a mixture of dibutyltin dilaurate and triethanolamine, and the like. The amount of the catalyst B may be, for example, 0.1 to 0.5 parts by mass, for example, 0.1 part by mass/0.3 part by mass/0.5 part by mass, based on 100 parts by mass of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester.
In one embodiment, in step S11, the molar ratio of the α, ω -hydroxyl terminated aliphatic diol to itaconic acid may be 1.15-1.25:1, such as 0.5mol of 2-methyl-1, 3-propanediol and 0.42mol of itaconic acid, and other formulations with a molar ratio of 1.15-1.25:1 are also possible and not limited.
In one embodiment, in step S11, itaconic acid and alpha, omega-hydroxyl terminated aliphatic diol monomer are subjected to melt polycondensation reaction at 150-190 ℃ for 10-12 hours. Wherein the pressure of the reaction system is gradually reduced, and the temperature of the reaction system is gradually increased. For example, firstly reacting for 3h at 150 ℃ and then reducing the system pressure to 0.8 Mpa; then heating to 170 ℃ for reaction for 2h and reducing the system pressure to 0.6 Mpa; then heating to 180 ℃ for reaction for 4 hours and reducing the system pressure to 0.4 Mpa; then the temperature is increased to 190 ℃ for reaction for 3h, and the system pressure is reduced to 0.2 Mpa.
In one embodiment, in step S11, after reacting itaconic acid with α, ω -hydroxyl-terminated aliphatic diol monomer for a period of time, for example, 3 hours, hydroquinone is added as a polymerization inhibitor, and the mass portion of hydroquinone may be, for example, 0.1 to 0.5 parts, for example, 0.1 part/0.3 part/0.5 part of hydroquinone is added based on 100 parts by mass of itaconic acid.
In one embodiment, in step S12, the mass part of N, N-dimethylformamide used for dissolving the reaction product may be 35 to 50 parts by mass, for example, based on 100 parts by mass of itaconic acid; the amount of xylene used for precipitation may be, for example, 350 to 500 parts by mass.
In one embodiment, after the xylene is added for precipitation in step S12, the precipitate may be washed and dried, for example, in a vacuum drying oven, for example, at a temperature of 70 to 90 ℃, for example, for 10 to 12 hours.
In one embodiment, in step S12, the hydroxyl value of the obtained product hydroxy-terminated itaconic acid-aliphatic glycol copolyester is, for example, 60-130mgKOH/g, and the molecular weight is, for example, 800-3000.
In one embodiment, in step S21, the molar ratio of the isocyanate group in the diisocyanate to the hydroxyl group in the hydroxyl-terminated itaconic acid-aliphatic diol copolyester may be 1.1 to 1.5:1, for example, 1.1:1/1.2:1/1.3:1/1.4:1/1.5: 1. For example, the mass of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester can be weighed, and then the required mass of the diisocyanate can be calculated according to the molar ratio of the isocyanate group in the diisocyanate to the hydroxyl group in the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester.
In a specific embodiment, in step S21, the diisocyanate may be one or more of isophorone diisocyanate and toluene diisocyanate, such as isophorone diisocyanate, toluene diisocyanate, and a mixture of isophorone diisocyanate and toluene diisocyanate.
In one embodiment, in step S22, before adding the photoinitiator, the reaction system may be cooled to room temperature, for example. The photoinitiator is, for example, one or more of 1-hydroxycyclohexylphenylketone, 2-hydroxy-methylphenylpropane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-one, benzophenone, such as 1-hydroxycyclohexylphenylketone, for example 2-hydroxy-methylphenylpropane-1-one, for example a mixture of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-one and benzophenone; the mass part of the photoinitiator is, for example, 2 to 5 parts, for example, 2 parts/3 parts/4 parts/5 parts of the photoinitiator, based on 100 parts of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester.
The invention will now be described by way of the following examples.
Example 1
A polyurethane type UV viscose reducing agent is prepared by the following steps:
(1) hydroxy-terminated itaconic acid-aliphatic diol copolyester
45.4g (0.50mol) of 2-methyl-1, 3-propanediol, 54.6g (0.42mol) of itaconic acid and 0.546g of strong acidic styrene cation exchange resin are weighed and added into a 1L reaction kettle, and N is introduced2Reacting at 150 deg.C for 3 hr, adding 0.0546g hydroquinone, and reducing system pressure to 0.8 Mpa; heating to 170 ℃ for reaction for 2h, and then reducing the system pressure to 0.6 MPa; heating to 180 ℃ for reaction for 4h, and then reducing the system pressure to 0.4 Mpa; heating to 190 deg.C, reacting for 3h, and reducing the system pressure to 0.2 Mpa. After the reaction is finished, cooling the reaction mixture to room temperature, adding 37.8g N N-dimethylformamide to dissolve the reaction mixture, precipitating the reaction mixture with 344g of xylene, and drying the precipitate in a vacuum drying oven at 85 ℃ for 10 hours to obtain the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester, wherein the hydroxyl value of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester is 126mgKOH/g, and the molecular weight of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester is 800.
(2) Preparation of polyurethane-type UV visbreaking adhesive
Weighing 100g of the hydroxyl-terminated itaconic acid-aliphatic diol copolyester prepared in the step (1), 62g of isophorone diisocyanate (IPDI) and 0.1g of dibutyltin dilaurate, placing the materials into a reactor, heating the reactor to 60 ℃, adding 300g of ethyl acetate, and reacting for 6 hours at 60 ℃; and then cooling to room temperature, adding 3g of 1-hydroxycyclohexyl phenyl ketone, and stirring for 1h to obtain the polyurethane type UV viscose reducer.
Example 2
A polyurethane type UV viscose reducing agent is prepared by the following steps:
(1) hydroxy-terminated itaconic acid-aliphatic diol copolyester
45.4g (0.50mol) of 1, 4-butanediol, 54.6g (0.42mol) of itaconic acid and 0.546g of strong acidic styrene cation exchange resin were weighed and added to a 1L reaction vessel, and N was introduced2Reacting at 150 deg.C for 3 hr, adding 0.0546g hydroquinone, and reducing system pressure to 0.8 Mpa; heating to 170 ℃ for reaction for 2h, and then reducing the system pressure to 0.6 MPa; heating to 180 ℃ for reaction for 4h, and then reducing the system pressure to 0.4 Mpa; heating to 190 deg.C, reacting for 3h, and reducing the system pressure to 0.2 Mpa. After the reaction is finished, cooling the reaction mixture to room temperature, adding 37.8g N N-dimethylformamide to dissolve the reaction mixture, precipitating the reaction mixture with 344g of xylene, and drying the precipitate in a vacuum drying oven at 85 ℃ for 10 hours to obtain the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester, wherein the hydroxyl value of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester is 120mgKOH/g, and the molecular weight of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester is 900.
(2) Preparation of polyurethane-type UV visbreaking adhesive
Weighing 100g of the hydroxyl-terminated itaconic acid-aliphatic diol copolyester prepared in the step (1), 62g of isophorone diisocyanate (IPDI) and 0.1g of dibutyltin dilaurate, placing the materials into a reactor, heating the reactor to 60 ℃, adding 300g of ethyl acetate, and reacting for 6 hours at 60 ℃; and then cooling to room temperature, adding 3g of 1-hydroxycyclohexyl phenyl ketone, and stirring for 1h to obtain the polyurethane type UV viscose reducer.
Example 3
A polyurethane type UV viscose reducing agent is prepared by the following steps:
(1) hydroxy-terminated itaconic acid-aliphatic diol copolyester
45.4g (0.50mol) of 2-methyl-1, 3-propanediol, 54.6g (0.42mol) of itaconic acid and 0.546g of strong acidic styrene cation exchange resin are weighed and added into a 1L reaction kettle, and N is introduced2Reacting at 150 deg.C for 3 hr, adding 0.0546g hydroquinone, and reducing system pressure to 0.8 Mpa; heating to 170 ℃ for reaction for 2h, and then pressing the systemThe force is reduced to 0.6 MPa; heating to 180 ℃ for reaction for 4h, and then reducing the system pressure to 0.4 Mpa; heating to 190 deg.C, reacting for 3h, and reducing the system pressure to 0.2 Mpa. After the reaction is finished, cooling the reaction mixture to room temperature, adding 37.8g N N-dimethylformamide to dissolve the reaction mixture, precipitating the reaction mixture with 344g of xylene, and drying the precipitate in a vacuum drying oven at 85 ℃ for 10 hours to obtain the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester, wherein the hydroxyl value of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester is 126mgKOH/g, and the molecular weight of the hydroxyl-terminated itaconic acid-aliphatic glycol copolyester is 800.
(2) Preparation of polyurethane-type UV visbreaking adhesive
Weighing 100g of the hydroxyl-terminated itaconic acid-aliphatic diol copolyester prepared in the step (1), 48.6g of Toluene Diisocyanate (TDI) and 0.1g of dibutyltin dilaurate, placing the materials in a reactor, heating the reactor to 60 ℃, adding 300g of ethyl acetate, and reacting for 6 hours at 60 ℃; and then cooling to room temperature, adding 3g of 1-hydroxycyclohexyl phenyl ketone, and stirring for 1h to obtain the polyurethane type UV viscose reducer.
Performance testing
The peel strength of the polyurethane-type UV degummed adhesive prepared in examples 1 to 4 is shown in table 1.
Table 1 table of 180 ° peel strength of UV detackifying adhesives of examples 1-4
Figure BDA0003248231990000091
As can be seen from the above table, the polyurethane type UV adhesive of the present invention does not cause the problem of adhesive residue adhesion on the device surface after the UV irradiation loses the adhesion. After the UV anti-sticking agent is irradiated by ultraviolet light, the 180-degree peel strength of the UV anti-sticking agent can be as low as 0.4N/25mm, the anti-sticking effect is obvious, and the UV anti-sticking agent is easy to peel. Before ultraviolet irradiation, the 180-degree peel strength of the UV adhesive can reach about 19N/25mm, the adhesive property is excellent, and wafers and the like can be effectively fixed.
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.

Claims (10)

1. The polyurethane type UV viscose reducer is characterized by having the following structural formula:
Figure FDA0003248231980000011
wherein R is1Is composed of
Figure FDA0003248231980000012
R is CnH2n，n＝3-5；
R2Is composed of
Figure FDA0003248231980000013
One kind of (1).
2. A preparation method of polyurethane type UV viscose reducer is characterized by comprising the following steps:
s1 itaconic acid and alpha, omega-hydroxyl-terminated aliphatic diol are synthesized into hydroxyl-terminated itaconic acid-aliphatic diol copolyester with a side chain containing double bonds;
the S2 hydroxyl-terminated itaconic acid-aliphatic diol copolyester reacts with diisocyanate to prepare polyurethane type adhesive, and then photoinitiator is added to obtain the polyurethane type UV viscose reducer.
3. The method according to claim 2, wherein step S1 includes:
adding a catalyst A into itaconic acid and an alpha, omega-hydroxyl-terminated aliphatic diol monomer, introducing nitrogen, reacting at 150-190 ℃ for 3-5 h, adding hydroquinone, and continuing to react for 5-7 h to obtain a reaction product;
dissolving the reaction product in N, N-dimethylformamide, and then adding xylene for precipitation to obtain hydroxyl-terminated itaconic acid-aliphatic diol copolyester;
the catalyst A is one or more of p-toluenesulfonic acid, tetrabutyl titanate and strong-acid styrene cation exchange resin.
4. The method according to claim 3, wherein in step S1, the molar ratio of the α, ω -hydroxyl terminated aliphatic diol to the itaconic acid is 1.15 to 1.25: 1.
5. The method according to claim 3, wherein in step S1, the pressure of the reaction system is gradually decreased and the temperature of the reaction system is gradually increased during the reaction of itaconic acid and the alpha, omega-hydroxyl terminated aliphatic diol monomer.
6. The preparation method of claim 3, wherein the hydroxyl-terminated itaconic acid-aliphatic diol copolyester has a hydroxyl value of 60-130mgKOH/g and a molecular weight of 800-3000.
7. The method according to claim 2, wherein step S2 includes:
dissolving hydroxyl-terminated itaconic acid-aliphatic diol copolyester in a solvent A, adding a catalyst B, introducing nitrogen for protection, then dripping diisocyanate, and reacting for 4-7 hours at the temperature of 60-80 ℃;
adding a photoinitiator after the reaction is finished and uniformly stirring to obtain the polyurethane type UV reduced adhesive;
the solvent A is one or more of ethyl acetate, acetone and tetrahydrofuran;
the catalyst B is one or more of dibutyltin dilaurate, stannous octoate, triethylene diamine and triethanolamine.
8. The polyurethane-based UV viscose reducer according to claim 5, wherein the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the hydroxyl-terminated itaconic acid-aliphatic diol copolyester is 1.1-1.5: 1.
9. The polyurethane-based UV viscose reducer according to claim 5, wherein said diisocyanate is one or more of isophorone diisocyanate and toluene diisocyanate.
10. The polyurethane-type UV viscose reducer according to claim 5, wherein said photoinitiator is one or more selected from 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-methyl phenyl propane-1-ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-ketone, and benzophenone.
CN202111038398.4A 2021-09-06 2021-09-06 Polyurethane type UV (ultraviolet) viscosity-reducing adhesive and preparation method thereof Active CN113736420B (en)

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CN109897590A (en) * 2019-02-15 2019-06-18 美瑞新材料股份有限公司 A kind of dual cure reaction type polyurethane hot-melt adhesive and its preparation method and application
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JP5460809B1 (en) * 2012-10-17 2014-04-02 古河電気工業株式会社 Adhesive tape for semiconductor processing
CN109897590A (en) * 2019-02-15 2019-06-18 美瑞新材料股份有限公司 A kind of dual cure reaction type polyurethane hot-melt adhesive and its preparation method and application
CN111995947A (en) * 2020-08-19 2020-11-27 长兴特殊材料（珠海）有限公司 Halogen-free chemical-resistant UV (ultraviolet) peelable adhesive and application thereof

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