CN106750154A - A kind of mercaptan modified polyurethane photocuring prepolymer and its preparation method and photocuring elastic coating prepared therefrom - Google Patents
A kind of mercaptan modified polyurethane photocuring prepolymer and its preparation method and photocuring elastic coating prepared therefrom Download PDFInfo
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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
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- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
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- 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
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- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a kind of mercaptan modified polyurethane photocuring prepolymer and its preparation method and photocuring elastic coating prepared therefrom, with following structural formula：Wherein：R1For： ；R2, R3, R5It is identical or different, it is independent of each other to be expressed as H or CH3；R4For： n1=1‑3；n2, n3=1‑4；m=1‑6.The present invention is modified by mercaptan to urethane acrylate, obtains that mercaptan modified polyurethane acrylate prepolymer has the advantages that laser curing velocity high, good, anti-wear performance is good for elasticity, good weatherability；Present invention process is first reacted with the mercaptan of various degrees of functionality with hydroxy acryl acid ester, eliminates sulfydryl, then is reacted and then blocked with hydroxy acryl acid ester, process is simple with isocyanates, is remained without sulfydryl in its finished product, and finished product is difficult gel.
Description
Technical field
The invention belongs to photo-curing material technical field, and in particular to a kind of mercaptan modified polyurethane photocuring prepolymer and
Its preparation method and photocuring elastic coating prepared therefrom.
Background technology
One of topmost component of UV cure systems is exactly photocuring performed polymer, and existing photocuring performed polymer typically has poly-
Urethane acrylate, polyester acrylate, epoxy acrylate etc..Due to polyurethane acrylate prepolymer composition, structure, property
Can degree of amplitude modulation it is big, cured product performance is excellent, has been a main class in photocuring prepolymer, but its curing rate it is more fast more
Hard crisp, it could be realized using generally needed to be added the fillers such as many elasticity powder in elastic handfeel coating, and performed polymer will
It is soft.The addition of the fillers such as excessive elastic powder can cause that its curing rate is slower, and crosslink density is relatively low, and surface drying is poor,
Scratch-resistant performance is also poor, and coating increase over time easily return it is viscous, surface become viscous hand, it is impossible to use.
Mercaptan is directly added in photocureable coating formula can improve curing rate, elasticity, crosslink density etc..But mercaptan
In exposed sulfydryl be very easy to and double bond occurs mikey addition reaction, cause finished product viscosity during holding to become big, solidifying
Glue, scrap.Particularly in transportation, the temperature in general summer packaging compartment can reach 80 degree, the UV containing mercaptan into
Product are very easy to gel.
The content of the invention
To solve the defect of above-mentioned prior art problem, primary and foremost purpose of the invention is to provide a kind of photocuring speed high
Degree, elastic, wear-resisting, good weatherability mercaptan modified polyurethane photocuring prepolymer.
Preparation method another object of the present invention is to provide above-mentioned mercaptan modified polyurethane photocuring prepolymer, the party
Method process is simple, without sulfydryl residual.
The present invention is to be achieved through the following technical solutions：
A kind of mercaptan modified polyurethane photocuring prepolymer, with following structural formula：
Wherein：R1For：
；
R2, R3, R5It is identical or different, it is independent of each other to be expressed as H or CH3；
R4For：
；
n1=1-3；
n2, n3=1-4；
m=1-6。
The preparation method of the above-mentioned mercaptan modified polyurethane photocuring prepolymer of the present invention, can be using in the following two kinds method
Any one preparation：
Method one：Comprise the following steps：
（1）The preparation of mercaptan modified polyalcohol：By weight, by 16~35 parts of mercaptan, 0.1~0.5 part of polymerization inhibitor and 0.1~
0.5 part of catalyst 1 is added in reaction vessel, is heated to 30~120 DEG C, is added dropwise and is added 15~30 parts of hydroxy acryl acid esters, is led to
Cooling water, reaction temperature control at 30~120 DEG C, completion of dropping, 30~120 DEG C are incubated 1 hour, and the whole reaction time is 3~8
Individual hour, discharging obtains mercaptan modified polyalcohol；Reaction equation is as follows：
Wherein,Represent mercaptan；R2, R3It is H or CH3；M is 1 to 6；n1For 1 to 3；n2For 1 to 4.
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 25~45 parts of isocyanates, 0.1~
0.5 part 2,0.1~0.5 part of polymerization inhibitor of catalyst is added in reaction vessel, is heated to 30~100 DEG C, is added dropwise to 10~30
Part hydroxy acryl acid ester, leads to cooling water, and reaction temperature control is at 30~100 DEG C, and completion of dropping, 30~100 DEG C of insulations 1 are small
When, the step of be dividedly in some parts 25~60 parts（1）The mercaptan modified polyalcohol for preparing, control temperature is reacted at 50~100 DEG C
Time is 3~8 hours, and detection %NCO is less than 0.1%, and discharging obtains mercaptan modified urethane acrylate.Reaction equation is as follows：
Wherein, R4For：
；
R5It is H or CH3；n3=1-4。
Method two：Comprise the following steps：
（1）The preparation of mercaptan modified polyalcohol：By weight, by 15~30 parts of hydroxy acryl acid esters, 0.1~0.5 part
Polymerization inhibitor and 0.1~0.5 part of catalyst 1 are added in reaction vessel, are heated to 30~120 DEG C, are added dropwise and are added 16~35 parts
Mercaptan, leads to cooling water, reaction temperature control at 30~120 DEG C, completion of dropping, 30~120 DEG C are incubated 1 hour, when entirely reacting
Between be 3~8 hours, discharging obtain mercaptan modified polyalcohol；Reaction equation is as follows：
Wherein,Represent mercaptan；R2, R3It is H or CH3；M is 1 to 6；n1For 1 to 3；n2For 1 to 4.
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 25~45 parts of isocyanates, 0.1~
0.5 part 2,0.1~0.5 part of polymerization inhibitor of catalyst is added in reaction vessel, is heated to 30~100 DEG C, is added dropwise to 25~60
Part step（1）The mercaptan modified polyalcohol for preparing, leads to cooling water, reaction temperature control at 30~100 DEG C, completion of dropping,
30~100 DEG C are incubated 1 hour, are dividedly in some parts 10~30 parts of hydroxy acryl acid esters, temperature are controlled at 50~100 DEG C, during reaction
Between be 3~8 hours, detection %NCO be less than 0.1%, discharging obtain mercaptan modified urethane acrylate, reaction equation is as follows：
R4For：
；
R5It is H or CH3；n3=1-4。
Described mercaptan is four（3- mercaptopropionic acids）Pentaerythritol ester, trimethylolpropane tris（3- mercaptopropionic acids）Ester, two
（3- mercaptopropionic acids）Glycol ester, four（3- TGAs）Pentaerythritol ester, trimethylolpropane tris（3- TGAs）Ester, two
（3- TGAs）Glycol ester, ethyoxyl trimethylolpropane tris（3- mercaptopropionic acids）Ester, 2.3- are double（It is thio（2- mercapto second
Base））- 1- n-propyl mercaptans, three（3- TGAs）Ethyl isocyanurate, dipentaerythritol（3- mercaptopropionic acids）Ester or four（3-
Mercaptobutyric acid）In pentaerythritol ester or several combinations.
Described hydroxy acryl acid ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, metering system
The combination of one or more in sour hydroxyl ethyl ester or hydroxy propyl methacrylate.
Described isocyanates is different hexamethylene diisocyanate, IPDI, two cyclohexyl methane two
The mixing of one or more in cyanate or cyclohexyl dimethylene diisocyanate.
Described catalyst 1 is triethylamine, triethanolamine, N, N- dipropyl -1- propylamine or N, in accelerine
The combination of one or more；Described catalyst 2 is one or more in organic tin catalyst or organo-bismuth class catalyst
Combination.
Described polymerization inhibitor is MEHQ, hydroquinones, 2- TBHQs or 2,5- di-t-butyl pair
The combination of one or more in benzenediol.
Reaction principle of the invention is：The present invention is first reacted with the mercaptan of various degrees of functionality with hydroxy acryl acid ester,
Sulfydryl is eliminated, then is reacted and then is blocked with hydroxy acryl acid ester with isocyanates, obtain mercaptan modified urethane acrylate
Performed polymer has the advantages that laser curing velocity high, elastic good, anti-wear performance be good, in good weatherability, and its finished product without sulfydryl residual,
Finished product is difficult gel.With four（3- mercaptopropionic acids）As a example by pentaerythritol ester, its synthetic reaction formula is as follows：
It is based on above-mentioned mercaptan modified polyurethane photocuring prepolymer present invention also offers a kind of photocuring elastic coating
Body, adds light trigger, reactive diluent, conven-tional adjuvants etc., and being made light by conventional production method well known in the art consolidates
Change elastic coating.
Described light trigger can be 1- hydroxycyclohexyl phenyl ketones 184,2- hydroxy-2-methyl -1- phenyl -1- third
In ketone 1173, α, α dimethoxys-α-phenyl acetophenone, α, α-diethoxy acetophenone, isopropyl phenyl -2- hydroxyls -2-
Methyl acetone, 2- methyl isophthalic acids-(4- first mercaptophenyl) -2- morpholine -1- acetone, 2- phenyl -2,2- dimethylaminos -1-
(4- morpholinyl phenyls) -1- butanone, 2,4,6- trimethylbenzoyls diethyl phosphonate, 2,4,6- trimethylbenzoyl diphenyl
Phosphine oxide, double (2,4,6 trimethylbenzoyl) phenyl phosphine oxides, double (2,6- dimethoxybenzoyls)-(4 ', 4 '-diformazans
Base octyl group -2) phosphine oxide, benzophenone, tetramethyl Michler's keton, 2- chlorothiaxanthenones, isopropyl thioxanthone and 2,4- diethyls
One or more in base thioxanthone.
The reactive diluent can be isobornyl thiocyanoacetate acrylate, acrylic acid morpholine, hy-droxybutyl or methyl-prop
The olefin(e) acid hydroxypropyl acrylate mixture of one or more.
The conven-tional adjuvants can be antioxidant 1010,168,1076,1035；Defoamer organic silicone oil etc..
The present invention compared with prior art, has the advantages that：
（1）The present invention is modified by mercaptan to urethane acrylate, is obtained mercaptan modified polyurethane acrylate prepolymer and is gathered
Body has the advantages that laser curing velocity high, elastic good, anti-wear performance be good, good weatherability；
（2）Present invention process is first reacted with the mercaptan of various degrees of functionality with hydroxy acryl acid ester, eliminates sulfydryl, then with isocyanide
Then acid esters reaction is blocked with hydroxy acryl acid ester, and process is simple is remained in its finished product without sulfydryl, and finished product is difficult to coagulate
Glue.
Specific embodiment
The present invention is further illustrated below by specific embodiment, following examples are the specific embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments, it is other any without departing from Spirit Essence of the invention
With the change, modification, replacement made under principle, combine, simplify, should be equivalent substitute mode, be included in of the invention
Within protection domain.
Embodiment 1：Four（3- mercaptopropionic acids）The synthesis of pentaerythritol ester modified urethane acrylate
（1）The preparation of mercaptan modified polyalcohol：By weight, by 30 part four（3- mercaptopropionic acids）Pentaerythritol ester, 0.3 part it is right
Hydroxyanisol and 0.3 part of triethylamine are added in reaction vessel, are heated to 80 DEG C, are added dropwise and are added 28.5 parts of hydroxy-ethyl acrylates,
Logical cooling water, reaction temperature control at 80 DEG C, completion of dropping, 80 DEG C are incubated 1 hour, and the whole reaction time is 5 hours, is discharged
To mercaptan modified polyalcohol A；Yield is 98.5%；1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）;
4.22 CH2（CH2-OCO）;2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 3.94 CH2{C-(CH2)4}。
Reaction equation is as follows：
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 30 parts of IPDIs
（IPDI）, 0.3 part organic tin catalyst, 0.3 part of MEHQ be added in reaction vessel, be heated to 80 DEG C, drop
Add 15.7 parts of hydroxy-ethyl acrylates, lead to cooling water, reaction temperature control at 80 DEG C, completion of dropping, 80 DEG C are incubated 1 hour, point
Criticize the step of adding 39 parts（1）The mercaptan modified polyalcohol A for preparing, at 60 DEG C, the reaction time is 5 hours to control temperature,
Detection %NCO is less than 0.1%, and discharging obtains mercaptan modified urethane acrylate, and yield is 99.6%.1HNMR(CDCl3,PPM)：δ
4.31 CH2（CH2-OCO）;2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 3.94 CH2{C-(CH2)4}；7.67 NH；
3.54 H (N-CH);1.08、1.33、1.42、1.67 CH2（On cycloaliphatic ring）；0.87、0.93 CH3（On cycloaliphatic ring）;
2.69、2.94 CH2（N- CH2）;6.76 NH; 4.31 CH2（CH2-OCO）;5.85、6.12、6.41 H(CH=CH2);4.38
CH2（CH2-OCO- CH=CH2）.
Reaction equation is as follows：
。
Embodiment 2：Trimethylolpropane tris（3- mercaptopropionic acids）The synthesis of ester modified urethane acrylate
（1）The preparation of mercaptan modified polyalcohol：By weight, by 25 parts of trimethylolpropane tris（3- mercaptopropionic acids）Ester, 0.2
Part MEHQ and 0.2 part of triethylamine are added in reaction vessel, are heated to 70 DEG C, are added dropwise and are added 24.5 parts of methacrylic acids
Hydroxyl ethyl ester, leads to cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour, and the whole reaction time is 6 small
When, discharging obtains mercaptan modified polyalcohol B;Yield 98.8%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-
OH）; 4.36 CH2（CH2-OCO）;2.70 CH（CHCO）; 2.65、2.90 CH2（CH2S）; 1.17 CH3（CH3-CH）;
2.83 CH2（CH2S）; 2.58 CH2（CH2-CO）； 3.94 CH2（C-CH2-OCO）;1.69 CH2（C-CH2）;0.83 CH3
（CH3-CH2-C）；
Reaction equation is as follows：
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 25 parts of IPDIs
（IPDI）, 0.3 part organic tin catalyst, 0.3 part of MEHQ be added in reaction vessel, be heated to 30~100
DEG C, be added dropwise to 13 parts of hydroxy-ethyl acrylates, lead to cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour,
The step of being dividedly in some parts 29.6 parts（1）The mercaptan modified polyalcohol B for preparing, at 50 DEG C, the reaction time is 8 small to control temperature
When, detection %NCO is less than 0.1%, and discharging obtains mercaptan modified urethane acrylate.Yield is 99.2%.1HNMR(CDCl3,
PPM)：δ4.36 CH2（CH2-OCO）;2.70 CH（CHCO）; 2.65、2.90 CH2（CH2S）; 1.17 CH3（CH3-CH）;
2.83 CH2（CH2S）; 2.58 CH2（CH2-CO）； 3.94 CH2（C-CH2-OCO）;1.69 CH2（C-CH2）;0.83 CH3
（CH3-CH2-C）; 7.67 NH；3.54 H (N-CH);1.08、1.33、1.42、1、67 CH2（On cycloaliphatic ring）；0.87、0.94
CH3（On cycloaliphatic ring）; 2.69、2.94 CH2（N- CH2）; 6.76 NH; 4.31 CH2（CH2-OCO）; 5.85、6.12、
6.41 H(CH=CH2);4.38 CH2（CH2-OCO- CH=CH2）.
Reaction equation is as follows：
Embodiment 3：Two（3- mercaptopropionic acids）The synthesis of glycol ester modified urethane acrylate
（1）The preparation of mercaptan modified polyalcohol：By weight, by 20 part two（3- mercaptopropionic acids）Glycol ester, 0.2 part it is right
Hydroxyanisol and 0.2 part of triethylamine are added in reaction vessel, are heated to 70 DEG C, are added dropwise and are added 19.5 parts of hydroxy-ethyl acrylates,
Logical cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour, and the whole reaction time is 6 hours, is discharged
To mercaptan modified polyalcohol C;Yield 99.3%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）; 4.22
CH2（CH2-OCO）;2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 4.31 CH2（CH2-OCO）；
Reaction equation is as follows：
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 25 parts of IPDIs
（IPDI）, 0.3 part organic tin catalyst, 0.3 part of MEHQ be added in reaction vessel, be heated to 30~100
DEG C, be added dropwise to 13 parts of hydroxy-ethyl acrylates, lead to cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour,
The step of being dividedly in some parts 26.5 parts（1）The mercaptan modified polyalcohol C for preparing, at 50 DEG C, the reaction time is 8 small to control temperature
When, detection %NCO is less than 0.1%, and discharging obtains mercaptan modified urethane acrylate.Yield is 99.1%.1HNMR(CDCl3,
PPM)：δ 5.85、6.12、6.41 H(CH=CH2); 4.38 CH2（CH2-OCO- CH=CH2）; 4.31 CH2（CH2-OCO）;
6.76 NH; 2.69、2.94 CH2（N- CH2）; 0.87、0.94 CH3（On cycloaliphatic ring）; 1.08、1.33、1.42、1、67
CH2（On cycloaliphatic ring）；3.54 H (N-CH); 7.67 NH; 4.31 CH2（CH2-OCO）；2.83 CH2（CH2S）;2.58 CH2
（CH2CO）.
Reaction equation is as follows：
Embodiment 4：Ethyoxyl trimethylolpropane tris（3- mercaptopropionic acids）The synthesis of ester modified urethane acrylate
（1）The preparation of mercaptan modified polyalcohol：By weight, by 25 parts of ethyoxyl trimethylolpropane tris（3- mercaptopropionic acids）
Ester, 0.2 part of MEHQ and 0.2 part of triethylamine are added in reaction vessel, are heated to 70 DEG C, are added dropwise and are added 16.4 parts of propylene
Sour hydroxyl ethyl ester, leads to cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour, and the whole reaction time is 6 small
When, discharging obtains mercaptan modified polyalcohol D;Yield 99.2%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-
OH）; 4.22 CH2（CH2-OC）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 4.2 CH2（CH2-OCO）; 3.63
CH2（CH2-O）; 3.79 CH2（C-CH2）; 1.69 CH2（C-CH2）; 0.83 CH3（CH3-CH2-C）.
Reaction equation is as follows：
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 25 parts of IPDIs
（IPDI）, 0.3 part organic tin catalyst, 0.3 part of MEHQ be added in reaction vessel, be heated to 70 DEG C, drop
Add 13 parts of hydroxy-ethyl acrylates, lead to cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour, in batches
The step of adding 33 parts（1）The mercaptan modified polyalcohol D for preparing, at 50 DEG C, the reaction time is 8 hours to control temperature, inspection
Survey %NCO and be less than 0.1%, discharging obtains mercaptan modified urethane acrylate.Yield is 99 %.1HNMR(CDCl3,PPM)：δ
5.85、6.12、6.41 H(CH=CH2);4.38 CH2（CH2-OCO- CH=CH2）；4.31 CH2（CH2-OCO）; 6.76 NH;
2.69、2.94 CH2（N- CH2）; 0.87、0.94 CH3（On cycloaliphatic ring）; 1.08、1.33、1.42、1、67 CH2（Cycloaliphatic ring
On）；3.54 H (N-CH); 7.67 NH；4.31 CH2（CH2-OC）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）;
4.2 CH2（CH2-OCO）; 3.63 CH2（CH2-O）; 3.79 CH2（C-CH2）; 1.69 CH2（C-CH2）; 0.83 CH3
（CH3-CH2-C）.
Reaction equation is as follows：
Embodiment 5：Three（3- TGAs）The synthesis of ethyl isocyanurate modified urethane acrylate
（1）The preparation of mercaptan modified polyalcohol：By weight, by 25 part three（3- TGAs）Ethyl isocyanurate, 0.2
Part MEHQ and 0.2 part of triethylamine are added in reaction vessel, are heated to 70 DEG C, are added dropwise and are added 16.6 parts of acrylic acid hydroxyl second
Ester, leads to cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour, and the whole reaction time is 6 hours, is gone out
Material obtains mercaptan modified polyol E;Yield 98.9%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）;
4.22 CH2（CH2-OC）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 4.51CH2（CH2-OCO）; 3.46 CH2
（CH2-N）.
Reaction equation is as follows：
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 25 parts of IPDIs
（IPDI）, 0.3 part organic tin catalyst, 0.3 part of MEHQ be added in reaction vessel, be heated to 70 DEG C, drop
Add 13 parts of hydroxy-ethyl acrylates, lead to cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour, in batches
The step of adding 33 parts（1）The mercaptan modified polyol E for preparing, at 50 DEG C, the reaction time is 8 hours to control temperature, inspection
Survey %NCO and be less than 0.1%, discharging obtains mercaptan modified urethane acrylate.Yield is 98.9 %.1HNMR(CDCl3,PPM)：δ
5.85、6.12、6.41 H(CH=CH2);4.38 CH2（CH2-OCO- CH=CH2）；4.31 CH2（CH2-OCO）; 6.76 NH;
2.69、2.94 CH2（N- CH2）; 0.87、0.94 CH3（On cycloaliphatic ring）; 1.08、1.33、1.42、1、67 CH2（Cycloaliphatic ring
On）；3.54 H (N-CH); 7.67 NH； 4.31 CH2（CH2-OCO）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）;
4.51CH2（CH2-OCO）; 3.46 CH2（CH2-N）.
Reaction equation is as follows：
Embodiment 6：Dipentaerythritol（3- mercaptopropionic acids）The synthesis of ester modified urethane acrylate
（1）The preparation of mercaptan modified polyalcohol：By weight, by 25 parts of dipentaerythritols（3- mercaptopropionic acids）Ester, 0.2 part it is right
Hydroxyanisol and 0.2 part of triethylamine are added in reaction vessel, are heated to 70 DEG C, are added dropwise and are added 22.3 parts of hydroxy-ethyl acrylates,
Logical cooling water, reaction temperature control at 70 DEG C, completion of dropping, 70 DEG C are incubated 1 hour, and the whole reaction time is 6 hours, is discharged
To mercaptan modified polyalcohol F;Yield 99.3%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）; 4.22
CH2（CH2-OC）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 3.94 CH2（CH2-C）.
Reaction equation is as follows：
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 30 parts of IPDIs
（IPDI）, 0.3 part organic tin catalyst, 0.3 part of MEHQ be added in reaction vessel, be heated to 80 DEG C, drop
Add 15.7 parts of hydroxy-ethyl acrylates, lead to cooling water, reaction temperature control at 80 DEG C, completion of dropping, 80 DEG C are incubated 1 hour, point
Criticize the step of adding 33.3 parts（1）The mercaptan modified polyalcohol A for preparing, at 60 DEG C, the reaction time is 5 small to control temperature
When, detection %NCO is less than 0.1%, and discharging obtains mercaptan modified urethane acrylate, and yield is 99 %.1HNMR(CDCl3,
PPM)：δ 5.85、6.12、6.41 H(CH=CH2);4.38 CH2（CH2-OCO- CH=CH2）；4.31 CH2（CH2-OCO）;
6.76 NH; 2.69、2.94 CH2（N- CH2）; 0.87、0.94 CH3（On cycloaliphatic ring）; 1.08、1.33、1.42、1、67
CH2（On cycloaliphatic ring）；3.54 H (N-CH); 7.67 NH；4.31 CH2（CH2-OCO）; 2.58 CH2（CH2CO）; 2.83
CH2（CH2S）; 3.94 CH2（CH2-C）.
Reaction equation is as follows：
Comparative example 1：By weight, by 30 parts of IPDI（IPDI）, 0.3 part triethylamine, 0.3 part it is right
Hydroxyanisol is added in reaction vessel, is heated to 30 DEG C, is added dropwise to 16.5 part four（3- mercaptopropionic acids）Pentaerythritol ester,
Finish, 70 DEG C are incubated 1 hour, add 15.7 parts of hydroxy-ethyl acrylates, lead to cooling water, reaction temperature is controlled at 100 DEG C, during reaction
Between be 10 hours, detection %NCO be less than 0.1%, discharging obtain four（3- mercaptopropionic acids）Pentaerythritol ester modified polyurethane acrylic acid
Ester, yield is 99.4%.
The mercaptan modified polyurethane photocuring prepolymer 95% that embodiment 1-6 and comparative example 1 are prepared, 5% is light-initiated
Agent heating for dissolving is uniform, its performance test its performance is tested after 300mj energy-curables, as a result as shown in table 1：
Table 1：The performance test results of mercaptan modified polyurethane photocuring prepolymer
Embodiment 7-12
Count by weight, the mercaptan modified polyurethane photocuring prepolymer for respectively preparing embodiment 1-6 and comparative example 1
65 parts, 5 parts of light trigger 1- hydroxycyclohexyl phenyl ketones, reactive diluent isobornyl thiocyanoacetate acrylate and hydroxyethyl methacrylate
Each 15 parts of propyl ester, mixing and stirring obtains photocuring elastic coating, tests its results of property as shown in table 2.
Table 2：The performance test results of photocuring elastic coating
Can be seen that the present invention by the performance test results of embodiment and obtain mercaptan modified polyurethane acrylate prepolymer has
The advantages of laser curing velocity high, good elastic good, anti-wear performance, good weatherability.Contrasted by embodiment 1 and comparative example 1 and can be seen that
Sulfydryl in comparative example 1 in mercaptan is directly with isocyanates reaction again with hydroxy acryl acid ester end-blocking, sulfydryl and isocyanates
Reaction needs with amines catalyst and sulfydryl easily has residual, so as to cause the easy gel of finished product and weather resistance compared with embodiment
1 is poor.
Each performance test methods or standard：
Yellowing resistance：ASTM G-151；
Elongation at break：GB3880-1997；
TAB is wear-resisting：ASTM-D1044.
Solidification energy：Solidification simultaneously be put into energy meter, survey its surface it is tack-free when energy.
Claims (9)
1. a kind of mercaptan modified polyurethane photocuring prepolymer, with following structural formula：
Wherein：R1For：
；
R2, R3, R5It is identical or different, it is independent of each other to be expressed as H or CH3；
R4For：
；
n1=1-3；
n2, n3=1-4；
m=1-6。
2. a kind of preparation method of mercaptan modified polyurethane photocuring prepolymer as claimed in claim 1, it is characterised in that bag
Include
Following steps：
（1）The preparation of mercaptan modified polyalcohol：By weight, by 16~35 parts of mercaptan, 0.1~0.5 part of polymerization inhibitor and 0.1~
0.5 part of catalyst 1 is added in reaction vessel, is heated to 30~120 DEG C, is added dropwise and is added 15~30 parts of hydroxy acryl acid esters, is led to
Cooling water, reaction temperature control at 30~120 DEG C, completion of dropping, 30~120 DEG C are incubated 1 hour, and the whole reaction time is 3~8
Individual hour, discharging obtains mercaptan modified polyalcohol；
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 25~45 parts of isocyanates, 0.1~0.5 part
2,0.1~0.5 part of polymerization inhibitor of catalyst be added in reaction vessel, be heated to 30~100 DEG C, be added dropwise to 10~30 parts containing hydroxyl
Base acrylate, leads to cooling water, reaction temperature control at 30~100 DEG C, completion of dropping, 30~100 DEG C are incubated 1 hour, in batches
The step of adding 25~60 parts（1）The mercaptan modified polyalcohol for preparing, at 50~100 DEG C, the reaction time is 3 to control temperature
~8 hours, detection %NCO is less than 0.1%, and discharging obtains mercaptan modified urethane acrylate.
3. a kind of preparation method of mercaptan modified polyurethane photocuring prepolymer as claimed in claim 1, it is characterised in that bag
Include
Following steps：
（1）The preparation of mercaptan modified polyalcohol：By weight, by 15~30 parts of hydroxy acryl acid esters, 0.1~0.5 part of resistance
Poly- agent and 0.1~0.5 part of catalyst 1 are added in reaction vessel, are heated to 30~120 DEG C, are added dropwise and are added 16~35 parts of mercaptan, are led to
Cooling water, reaction temperature control at 30~120 DEG C, completion of dropping, 30~120 DEG C are incubated 1 hour, and the whole reaction time is 3~8
Individual hour, discharging obtains mercaptan modified polyalcohol；
（2）The preparation of mercaptan modified urethane acrylate：By weight, by 25~45 parts of isocyanates, 0.1~0.5 part
2,0.1~0.5 part of polymerization inhibitor of catalyst be added in reaction vessel, be heated to 30~100 DEG C, be added dropwise to 25~60 parts of steps
（1）The mercaptan modified polyalcohol for preparing, leads to cooling water, and reaction temperature is controlled in 30~100 DEG C, completion of dropping, 30~100
DEG C insulation 1 hour, is dividedly in some parts 10~30 parts of hydroxy acryl acid esters, and at 50~100 DEG C, the reaction time is 3~8 to control temperature
Individual hour, detection %NCO is less than 0.1%, and discharging obtains mercaptan modified urethane acrylate.
4. the preparation method of the mercaptan modified polyurethane photocuring prepolymer according to Claims 2 or 3, it is characterised in that
Described mercaptan is four（3- mercaptopropionic acids）Pentaerythritol ester, trimethylolpropane tris（3- mercaptopropionic acids）Ester, two（3- sulfydryls third
Acid）Glycol ester, four（3- TGAs）Pentaerythritol ester, trimethylolpropane tris（3- TGAs）Ester, two（3- sulfydryl second
Acid）Glycol ester, ethyoxyl trimethylolpropane tris（3- mercaptopropionic acids）Ester, 2.3- are double（It is thio（2- mercapto ethyls））- 1- positive third
Mercaptan, three（3- TGAs）Ethyl isocyanurate, dipentaerythritol（3- mercaptopropionic acids）Ester or four（3- mercaptobutyric acids）Season
In Doutrate or several combinations.
5. the preparation method of the mercaptan modified polyurethane photocuring prepolymer according to Claims 2 or 3, it is characterised in that
Described hydroxy acryl acid ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate
Or the combination of one or more in hydroxy propyl methacrylate.
6. the preparation method of the mercaptan modified polyurethane photocuring prepolymer according to Claims 2 or 3, it is characterised in that
Described isocyanates be hexamethylene diisocyanate, IPDI, two cyclohexyl methane diisocyanates or
The mixing of one or more in cyclohexyl dimethylene diisocyanate.
7. the preparation method of the mercaptan modified polyurethane photocuring prepolymer according to Claims 2 or 3, it is characterised in that
Described catalyst 1 is triethylamine, triethanolamine, N, N- dipropyl -1- propylamine or N, the one kind or several in accelerine
The combination planted；Described catalyst 2 is the combination of one or more in organic tin catalyst or organo-bismuth class catalyst.
8. the preparation method of the mercaptan modified polyurethane photocuring prepolymer according to Claims 2 or 3, it is characterised in that
Described polymerization inhibitor is in MEHQ, hydroquinones, 2- TBHQs or 2,5- di-tert-butyl hydroquinone
The combination of one or more.
9. a kind of photocuring elastic coating, comprising the mercaptan modified polyurethane photocuring prepolymer described in claim 1.
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