CN107698737A - A kind of three-functionality-degree urethane acrylate of silicone-containing segment and preparation method thereof - Google Patents

A kind of three-functionality-degree urethane acrylate of silicone-containing segment and preparation method thereof Download PDF

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Publication number
CN107698737A
CN107698737A CN201711068602.0A CN201711068602A CN107698737A CN 107698737 A CN107698737 A CN 107698737A CN 201711068602 A CN201711068602 A CN 201711068602A CN 107698737 A CN107698737 A CN 107698737A
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silicone
functionality
urethane acrylate
isocyanate groups
performed polymer
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宋彩雨
孙明明
薛刚
张斌
张绪刚
李坚辉
王磊
赵明
刘彩召
李奇力
梅格
徐博
杨艳晶
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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    • 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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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Abstract

A kind of three-functionality-degree urethane acrylate of silicone-containing segment and preparation method thereof, it is related to a kind of urethane acrylate and preparation method thereof.The invention aims to solve the problems, such as poor existing urethane acrylate weatherability, pliability and elongation is bad and organosilicon polyurethane acrylate laser curing velocity is slow.A kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment：First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized；2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized；3rd, trihydroxylic alcohol is well mixed with one end for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, reacts 1h~3h.Excellent in mechanical performance of the three-functionality-degree urethane acrylate of silicone-containing segment prepared by the present invention after photocuring.The present invention can obtain a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment.

Description

A kind of three-functionality-degree urethane acrylate of silicone-containing segment and preparation method thereof
Technical field
The present invention relates to a kind of urethane acrylate and preparation method thereof.
Background technology
Urethano in urethane acrylate oligomer structure, there is very high active and very strong polarity, for rubber The multiple materials such as glue, metal, fabric, leather, paper, timber, ceramics, glass, plastics have excellent adhesive property.Polyurethane Hydrogen bond can be formed between macromolecular chain or between adherend, molcohesion is strong, makes adhesive strength higher, shows excellent Pliability, shock resistance and scrape stability.Acrylate-functional groups are solid rapidly after ultraviolet lighting under light trigger effect Change, protrude this quasi-oligomer application performance in UV curing field.
Siloxane oligomer shows high-low temperature resistant and excellent chemistry is steady because of its unique Si-O-Si backbone structure Qualitative, electrical insulation capability is excellent, while has prominent ageing-resistant performance, and good elasticity is kept within the scope of wider temperature The advantages that.But there is also intensity difference, hardness is small, adhesive force is small, the curing reaction time is long, temperature is high the shortcomings of, single silicon Oxygen alkane oligomer is difficult to meet some special requirements.The compatibility of siloxane oligomer and other resins is poor, it is difficult to Preferable material is obtained by simple blending and modifying.Siloxanes segment is incorporated into urethane acrylate structure, not only The original ultraviolet light ability to cure of polyurethane material and excellent application performance can be kept, moreover it is possible to obtain higher weatherability and Heat endurance, obtain the ultraviolet photocureable material of high comprehensive performance.
The method of existing urethane acrylate oligomer is solvent method, solvent method easily, high conversion rate, reaction it is easy Control, obtained product viscosity is low, application technology relative maturity, but solvent removal is difficult after reaction, the easy xanthochromia of resin, not ring Protect.It is bad poor weatherability, pliability and elongation to be also present in existing urethane acrylate, organosilicon polyurethane acrylate light The problem of curing rate is slow.
The content of the invention
It is bad and have the invention aims to solve poor existing urethane acrylate weatherability, pliability and elongation The slow-paced problem of machine silicon polyurethane propenoic acid ester photocureable, and a kind of three-functionality-degree polyurethane of silicone-containing segment is provided Acrylate and preparation method thereof.
A kind of structural formula of the three-functionality-degree urethane acrylate of silicone-containing segment is：
Wherein described R isMiddle n value model Enclose for 1~4；Described R1For Described R2For Middle a span is 6~20,Middle b's takes It is 2~35 to be worth scope；Described R3For
A kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment, it is specifically complete according to the following steps Into：
First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized：
Terminal hydroxy group siloxane oligomer is well mixed with diisocyanate, then is warming up to 40 DEG C~60 DEG C, then in temperature To react 3h~5h at 40 DEG C~60 DEG C, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is obtained；
The mol ratio of terminal hydroxy group siloxane oligomer and diisocyanate described in step 1 is 1:(2~2.3)；
2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized：
Hydroxy acrylate is mixed with both ends for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups It is even, then 50 DEG C~70 DEG C are warming up to, then 1h~3h is reacted at being 50 DEG C~70 DEG C in temperature, it is isocyanate groups to obtain one end Silicone-containing segmented polyurethane performed polymer II；
Hydroxy acrylate and both ends described in step 2 is pre- for the silicone-containing segmented polyurethane of isocyanate groups The mol ratio of aggressiveness I is (1~1.2):1；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment is synthesized：
Trihydroxylic alcohol is well mixed with one end for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then risen Temperature reacts 1h~3h to 60 DEG C~80 DEG C, then at being 60 DEG C~80 DEG C in temperature, and the three-functionality-degree for obtaining silicone-containing segment gathers Urethane acrylate；
Silicone-containing segmented polyurethane performed polymer II of the trihydroxylic alcohol with one end for isocyanate groups described in step 3 Mol ratio be 1:(3~3.05).
The principle and advantage of the present invention：
First, the three-functionality-degree urethane acrylate of silicone-containing segment prepared by the present invention has three-functionality-degree reactive group Group, molecule double bond density is higher, light trigger effect under, after ultraviolet light irradiation can rapid curing, formed cross-linked network, And obtain higher crosslink density；Simultaneously containing acrylate-functional groups and highly polar amino-formate bond, have after solidification High-wearing feature, adhesion, pliability, high-peeling strength and the excellent resistance to low temperature and polyacrylate of polyurethane are remarkable Optical property and weatherability, be a kind of radiation curing material of high comprehensive performance；
2nd, the siloxanes segment in the three-functionality-degree urethane acrylate of silicone-containing segment prepared by the present invention is rule Whole polydimethylsiloxane structural, there is weatherability, height temperature stability, hydrophobicity and good chemical stability, shearing resistance Cut ability and electrical insulation capability is excellent；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment prepared by the present invention and a variety of polyurethane acroleic acids Ester oligomer or acrylate monomer intersolubility are good；
4th, the reaction condition for the three-functionality-degree urethane acrylate that the present invention prepares silicone-containing segment is gentle, yield Height, yield are 89%~96%, and preparation process is easy to operate, and the three-functionality-degree urethane acrylate of silicone-containing segment is deposited Storage is convenient；
5th, the three-functionality-degree urethane acrylate of silicone-containing segment prepared by the present invention can be used directly, and radiate The fields such as cured adhesive, coating, printing have potential value；
6th, mechanical property of the three-functionality-degree urethane acrylate of silicone-containing segment prepared by the present invention after photocuring Can be excellent, linear shrinkage is relatively low.
The present invention can obtain a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the three-functionality-degree urethane acrylate of silicone-containing segment prepared by embodiment one.
Embodiment
Embodiment one：Present embodiment is a kind of three-functionality-degree urethane acrylate of silicone-containing segment Structural formula is：
Wherein described R isMiddle n value model Enclose for 1~4；Described R1For Described R2For Middle a span is 6~20,Middle b value Scope is 2~35；Described R3For
Embodiment two：Present embodiment is a kind of three-functionality-degree urethane acrylate of silicone-containing segment What preparation method was specifically realized by the following steps：
First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized：
Terminal hydroxy group siloxane oligomer is well mixed with diisocyanate, then is warming up to 40 DEG C~60 DEG C, then in temperature To react 3h~5h at 40 DEG C~60 DEG C, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is obtained；
The mol ratio of terminal hydroxy group siloxane oligomer and diisocyanate described in step 1 is 1:(2~2.3)；
2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized：
Hydroxy acrylate is mixed with both ends for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups It is even, then 50 DEG C~70 DEG C are warming up to, then 1h~3h is reacted at being 50 DEG C~70 DEG C in temperature, it is isocyanate groups to obtain one end Silicone-containing segmented polyurethane performed polymer II；
Hydroxy acrylate and both ends described in step 2 is pre- for the silicone-containing segmented polyurethane of isocyanate groups The mol ratio of aggressiveness I is (1~1.2):1；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment is synthesized：
Trihydroxylic alcohol is well mixed with one end for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then risen Temperature reacts 1h~3h to 60 DEG C~80 DEG C, then at being 60 DEG C~80 DEG C in temperature, and the three-functionality-degree for obtaining silicone-containing segment gathers Urethane acrylate；
Silicone-containing segmented polyurethane performed polymer II of the trihydroxylic alcohol with one end for isocyanate groups described in step 3 Mol ratio be 1:(3~3.05).
The principle and advantage of present embodiment：
First, the three-functionality-degree urethane acrylate of silicone-containing segment prepared by present embodiment has three-functionality-degree anti- Answer group, molecule double bond density is higher, light trigger effect under, after ultraviolet light irradiation can rapid curing, formed crosslinking Network, and obtain higher crosslink density；Simultaneously containing acrylate-functional groups and highly polar amino-formate bond, after solidification High-wearing feature, adhesion, pliability, high-peeling strength and excellent resistance to low temperature and polyacrylate with polyurethane Remarkable optical property and weatherability, is a kind of radiation curing material of high comprehensive performance；
2nd, the siloxanes segment in the three-functionality-degree urethane acrylate of silicone-containing segment prepared by present embodiment For regular polydimethylsiloxane structural, there is weatherability, height temperature stability, hydrophobicity and good chemical stability, Anti-shear ability and electrical insulation capability are excellent；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment prepared by present embodiment and a variety of polyurethane third Olefin(e) acid ester oligomer or acrylate monomer intersolubility are good；
4th, present embodiment prepare the three-functionality-degree urethane acrylate of silicone-containing segment reaction condition it is gentle, Yield is high, and yield is 89%~96%, and preparation process is easy to operate, and the three-functionality-degree urethane acrylate of silicone-containing segment Convenient storage；
5th, the three-functionality-degree urethane acrylate of silicone-containing segment prepared by present embodiment can be used directly, The fields such as radiation curable adhesive, coating, printing have potential value；
6th, power of the three-functionality-degree urethane acrylate of silicone-containing segment prepared by present embodiment after photocuring Excellent performance is learned, linear shrinkage is relatively low.
Present embodiment can obtain a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment.
Embodiment three：The difference of present embodiment and embodiment two is：End described in step 1 Hydrosiloxane oligomer is the mixture of one or both of hydroxy silicon oil and hydroxypropyl silicone oil；Described hydroxy silicon oil Molal weight is 400g/mol~5000g/mol；The molal weight of described hydroxypropyl silicone oil is 1000g/mol~3000g/ mol.Other steps are identical with embodiment two.
Embodiment four：Present embodiment is with one of embodiment two to three difference：Institute in step 1 The diisocyanate stated is one kind or wherein several mixtures in TDI, MDI, IPDI, HDI, HMDI and HTDI.Other steps Suddenly it is identical with embodiment two to three.
Embodiment five：Present embodiment is with one of embodiment two to four difference：Institute in step 2 The hydroxy acrylate stated is hydroxy propyl methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and acrylic acid hydroxyl second One kind or wherein several mixtures in ester.Other steps are identical with embodiment two to four.
Embodiment six：Present embodiment is with one of embodiment two to five difference：Institute in step 3 The trihydroxylic alcohol stated is trimethylolpropane, glycerine and one kind in polycaprolactone trihydroxylic alcohol or wherein several mixtures；Institute The molal weight for the polycaprolactone trihydroxylic alcohol stated is 200g/mol~1000g/mol.Other steps and embodiment two to Five is identical.
Embodiment seven：Present embodiment is with one of embodiment two to six difference：Will in step 1 Terminal hydroxy group siloxane oligomer is well mixed with diisocyanate, then is warming up to 40 DEG C~50 DEG C, then temperature be 40 DEG C~50 3h~4h is reacted at DEG C, obtains the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups.Other steps and tool Body embodiment two to six is identical.
Embodiment eight：Present embodiment is with one of embodiment two to seven difference：Will in step 2 Hydroxy acrylate is well mixed with both ends for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups, then is warming up to 50 DEG C~60 DEG C, then 1h~2h is reacted at being 50 DEG C~60 DEG C in temperature, obtain the silicone-containing that one end is isocyanate groups Segmented polyurethane performed polymer II.Other steps are identical with embodiment two to seven.
Embodiment nine：Present embodiment is with one of embodiment two to eight difference：Will in step 3 Trihydroxylic alcohol and one end are well mixed for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then be warming up to 60 DEG C~ 70 DEG C, then 1h~2h is reacted at being 60 DEG C~70 DEG C in temperature, obtain the three-functionality-degree polyurethane acroleic acid of silicone-containing segment Ester.Other steps are identical with embodiment two to eight.
Embodiment ten：Present embodiment is with one of embodiment two to nine difference：Institute in step 1 The terminal hydroxy group siloxane oligomer and the mol ratio of diisocyanate stated are 1:(2.1~2.2).Other steps and specific embodiment party Formula two to nine is identical.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment, is specifically pressed What following steps were completed：
First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized：
100g terminal hydroxy groups siloxane oligomer is well mixed with 33.64g diisocyanate, then is warming up to 50 DEG C, then Temperature is to react 4h at 50 DEG C, obtains the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups；
Terminal hydroxy group siloxane oligomer described in step 1 is hydroxypropyl silicone oil；Mole matter of described hydroxypropyl silicone oil Measure as 1000g/mol；
Diisocyanate described in step 1 is HDI；
2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized：By 14.32g acrylic acid Hydroxypropyl acrylate is well mixed with the both ends obtained in step 1 for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups, 60 DEG C are warming up to again, then reacts 2h at being 60 DEG C in temperature, obtain the poly- ammonia of silicone-containing segment that one end is isocyanate groups Ester performed polymer II；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment is synthesized：By in 16.67g trihydroxylic alcohols and step 2 Obtained one end is well mixed for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then is warming up to 70 DEG C, then 2h is reacted at being 70 DEG C in temperature, obtains the three-functionality-degree urethane acrylate of silicone-containing segment；
Trihydroxylic alcohol described in step 3 is polycaprolactone trihydroxylic alcohol；The molal weight of described polycaprolactone trihydroxylic alcohol is 500g/mol。
A kind of structural formula of three-functionality-degree urethane acrylate of silicone-containing segment prepared by embodiment one is：
Fig. 1 is the infrared spectrogram of the three-functionality-degree urethane acrylate of silicone-containing segment prepared by embodiment one.
From fig. 1, it can be seen that in 3350cm-1Locate the characteristic absorption peak for-NH, 2267cm-1- NCO the characteristic absorption peaks at place are complete Disappear, 1720cm-1Locate the characteristic absorption peak for C=O, 810cm-1Locate as C=C characteristic absorption peaks, it was demonstrated that synthesized for target Product.
Embodiment two：A kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment, is specifically pressed What following steps were completed：
First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized：
100g terminal hydroxy groups siloxane oligomer is well mixed with 40.42g diisocyanate, then is warming up to 45 DEG C, then Temperature is to react 4h at 45 DEG C, obtains the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups；
Terminal hydroxy group siloxane oligomer described in step 1 is hydroxy silicon oil；The molal weight of described hydroxy silicon oil is 1100g/mol；
Diisocyanate described in step 1 is IPDI；
2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized：By 13.11g hydroxyls third Olefin(e) acid ester is well mixed with the both ends obtained in step 1 for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups, 60 DEG C are warming up to again, then reacts 2h at being 60 DEG C in temperature, obtain the poly- ammonia of silicone-containing segment that one end is isocyanate groups Ester performed polymer II；
Hydroxy acrylate described in step 2 is hydroxy propyl methacrylate；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment is synthesized：By in 15.16g trihydroxylic alcohols and step 2 Obtained one end is well mixed for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then is warming up to 70 DEG C, then 2h is reacted at being 70 DEG C in temperature, obtains the three-functionality-degree urethane acrylate of silicone-containing segment；
Trihydroxylic alcohol described in step 3 is polycaprolactone trihydroxylic alcohol；The molal weight of described polycaprolactone trihydroxylic alcohol is 500g/mol。
A kind of structural formula of three-functionality-degree urethane acrylate of silicone-containing segment prepared by embodiment two is：
Embodiment three：A kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment, is specifically pressed What following steps were completed：
First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized：
100g terminal hydroxy groups siloxane oligomer is well mixed with 17.42g diisocyanate, then is warming up to 40 DEG C, then Temperature is to react 4h at 40 DEG C, obtains the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups；
Terminal hydroxy group siloxane oligomer described in step 1 is hydroxypropyl silicone oil；Mole matter of described hydroxypropyl silicone oil Measure as 2000g/mol；
Diisocyanate described in step 1 is TDI；
2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized：By 12.20g hydroxyls third Olefin(e) acid ester is well mixed with the both ends obtained in step 1 for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups, 65 DEG C are warming up to again, then reacts 3h at being 65 DEG C in temperature, obtain the poly- ammonia of silicone-containing segment that one end is isocyanate groups Ester performed polymer II；
Hydroxy acrylate described in step 2 is hydroxy-ethyl acrylate；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment is synthesized：It will be obtained in 3.02g trihydroxylic alcohols and step 2 The one end arrived is well mixed for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then is warming up to 60 DEG C, then Temperature is to react 3h at 60 DEG C, obtains the three-functionality-degree urethane acrylate of silicone-containing segment；
Trihydroxylic alcohol described in step 3 is glycerine.
A kind of structural formula of three-functionality-degree urethane acrylate of silicone-containing segment prepared by embodiment three is：
Example IV：A kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment, is specifically pressed What following steps were completed：
First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized：
100g terminal hydroxy groups siloxane oligomer is well mixed with 45.51g diisocyanate, then is warming up to 50 DEG C, then Temperature is to react 5h at 50 DEG C, obtains the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups；
Terminal hydroxy group siloxane oligomer described in step 1 is hydroxy silicon oil；The molal weight of described hydroxy silicon oil is 1100g/mol；
Diisocyanate described in step 1 is MDI；
2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized：By 12.43g hydroxyls third Olefin(e) acid ester is well mixed with the both ends obtained in step 1 for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups, 50 DEG C are warming up to again, then reacts 3h at being 50 DEG C in temperature, obtain the poly- ammonia of silicone-containing segment that one end is isocyanate groups Ester performed polymer II；
Hydroxy acrylate described in step 2 is hydroxypropyl acrylate；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment is synthesized：It will be obtained in 4.06g trihydroxylic alcohols and step 2 The one end arrived is well mixed for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then is warming up to 60 DEG C, then Temperature is to react 2h at 60 DEG C, obtains the three-functionality-degree urethane acrylate of silicone-containing segment；
Trihydroxylic alcohol described in step 3 is trimethylolpropane.
A kind of structural formula of three-functionality-degree urethane acrylate of silicone-containing segment prepared by example IV is：
Embodiment five：A kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment, is specifically pressed What following steps were completed：
First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized：
200g terminal hydroxy groups siloxane oligomer is well mixed with 33.37g diisocyanate, then is warming up to 50 DEG C, then Temperature is to react 4h at 50 DEG C, obtains the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups；
Terminal hydroxy group siloxane oligomer described in step 1 is hydroxy silicon oil；The molal weight of described hydroxy silicon oil is 3000g/mol；
Diisocyanate described in step 1 is MDI；
2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized：By 7.74g hydroxies Acid esters is well mixed with the both ends obtained in step 1 for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups, then 50 DEG C are warming up to, then 3h is reacted at being 50 DEG C in temperature, obtains the silicone-containing segmented polyurethane that one end is isocyanate groups Performed polymer II；
Hydroxy acrylate described in step 2 is hydroxy-ethyl acrylate；
3rd, the three-functionality-degree urethane acrylate of silicone-containing segment is synthesized：It will be obtained in 2.99g trihydroxylic alcohols and step 2 The one end arrived is well mixed for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then is warming up to 60 DEG C, then Temperature is to react 3h at 60 DEG C, obtains the three-functionality-degree urethane acrylate of silicone-containing segment；
Trihydroxylic alcohol described in step 3 is trimethylolpropane.
A kind of structural formula of three-functionality-degree urethane acrylate of silicone-containing segment prepared by embodiment five is：
The three-functionality-degree urethane acrylate for the silicone-containing segment that embodiment one is prepared to embodiment five is through photocuring Excellent in mechanical performance afterwards, linear shrinkage is relatively low, with acrylate monomer intersolubility.

Claims (10)

  1. A kind of a kind of 1. three-functionality-degree urethane acrylate of silicone-containing segment, it is characterised in that the three of silicone-containing segment The structural formula of degree of functionality urethane acrylate is：
    Wherein Described R isMiddle n span is 1 ~4；Described R1For Described R2For Middle a span is 6~20,Middle b value Scope is 2~35；Described R3For
  2. 2. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment as claimed in claim 1, its It is specifically complete according to the following steps to be characterised by a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment Into：
    First, the silicone-containing segmented polyurethane performed polymer I that both ends are isocyanate groups is synthesized：
    Terminal hydroxy group siloxane oligomer is well mixed with diisocyanate, then is warming up to 40 DEG C~60 DEG C, then temperature be 40 DEG C~60 DEG C at react 3h~5h, obtain both ends be isocyanate groups silicone-containing segmented polyurethane performed polymer I；
    The mol ratio of terminal hydroxy group siloxane oligomer and diisocyanate described in step 1 is 1:(2~2.3)；
    2nd, the silicone-containing segmented polyurethane performed polymer II that one end is isocyanate groups is synthesized：
    Hydroxy acrylate is well mixed with both ends for the silicone-containing segmented polyurethane performed polymer I of isocyanate groups, then 50 DEG C~70 DEG C are warming up to, then 1h~3h is reacted at being 50 DEG C~70 DEG C in temperature, it is containing for isocyanate groups to obtain one end Siloxanes segment base polyurethane prepolymer for use as II；
    Silicone-containing segmented polyurethane performed polymer I of the hydroxy acrylate with both ends for isocyanate groups described in step 2 Mol ratio be (1~1.2):1；
    3rd, the three-functionality-degree urethane acrylate of silicone-containing segment is synthesized：
    Trihydroxylic alcohol is well mixed with one end for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups, then is warming up to 60 DEG C~80 DEG C, then 1h~3h is reacted at being 60 DEG C~80 DEG C in temperature, obtain the three-functionality-degree polyurethane of silicone-containing segment Acrylate；
    Trihydroxylic alcohol described in step 3 the rubbing for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups with one end You are than being 1:(3~3.05).
  3. 3. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment according to claim 1, It is characterized in that the terminal hydroxy group siloxane oligomer described in step 1 is hydroxy silicon oil and one kind in hydroxypropyl silicone oil or two The mixture of kind；The molal weight of described hydroxy silicon oil is 400g/mol~5000g/mol；Described hydroxypropyl silicone oil rubs Your quality is 1000g/mol~3000g/mol.
  4. 4. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment according to claim 1, It is characterized in that the diisocyanate described in step 1 is for one kind in TDI, MDI, IPDI, HDI, HMDI and HTDI or wherein Several mixtures.
  5. 5. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment according to claim 1, It is characterized in that the hydroxy acrylate described in step 2 is hydroxy propyl methacrylate, hydroxypropyl acrylate, metering system One kind or wherein several mixtures in sour hydroxyl ethyl ester and hydroxy-ethyl acrylate.
  6. 6. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment according to claim 1, It is characterized in that trihydroxylic alcohol described in step 3 is trimethylolpropane, glycerine and one kind in polycaprolactone trihydroxylic alcohol or Wherein several mixtures；The molal weight of described polycaprolactone trihydroxylic alcohol is 200g/mol~1000g/mol.
  7. 7. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment according to claim 1, It is characterized in that being well mixed terminal hydroxy group siloxane oligomer with diisocyanate in step 1, then it is warming up to 40 DEG C~50 DEG C, then 3h~4h is reacted at being 40 DEG C~50 DEG C in temperature, obtain the poly- ammonia of silicone-containing segment that both ends are isocyanate groups Ester performed polymer I.
  8. 8. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment according to claim 1, It is characterized in that the silicone-containing segmented polyurethane pre-polymerization in step 2 by hydroxy acrylate with both ends for isocyanate groups Body I is well mixed, then is warming up to 50 DEG C~60 DEG C, then reacts 1h~2h at being 50 DEG C~60 DEG C in temperature, and it is different to obtain one end The silicone-containing segmented polyurethane performed polymer II of cyanate group.
  9. 9. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment according to claim 1, It is characterized in that trihydroxylic alcohol is mixed with one end for the silicone-containing segmented polyurethane performed polymer II of isocyanate groups in step 3 Close uniformly, then be warming up to 60 DEG C~70 DEG C, then 1h~2h is reacted at being 60 DEG C~70 DEG C in temperature, obtain silicone-containing segment Three-functionality-degree urethane acrylate.
  10. 10. a kind of preparation method of the three-functionality-degree urethane acrylate of silicone-containing segment according to claim 1, It is characterized in that the mol ratio of the terminal hydroxy group siloxane oligomer and diisocyanate described in step 1 is 1:(2.1~2.2).
CN201711068602.0A 2017-11-02 2017-11-02 A kind of three-functionality-degree urethane acrylate of silicone-containing segment and preparation method thereof Pending CN107698737A (en)

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CN113354791A (en) * 2021-06-24 2021-09-07 哈尔滨工业大学无锡新材料研究院 UV-curable hyperbranched fluorine-silicon modified polyurethane, preparation method thereof and coating prepared from polyurethane
EP4134387A1 (en) 2021-08-11 2023-02-15 Covestro Deutschland AG Polyol composition
CN113831459A (en) * 2021-09-28 2021-12-24 泉州师范学院 Low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing and preparation method thereof
CN113845623A (en) * 2021-09-28 2021-12-28 泉州师范学院 Low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chain for photocuring 3D printing and preparation method thereof
CN113831459B (en) * 2021-09-28 2023-10-10 泉州师范学院 Low-temperature-resistant photo-curing flexible photosensitive resin composition for 3D printing and preparation method thereof

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