CN106519182A - Organic silicon modified polyurethane acrylate oligomer, and preparation method thereof - Google Patents
Organic silicon modified polyurethane acrylate oligomer, and preparation method thereof Download PDFInfo
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- CN106519182A CN106519182A CN201611014616.XA CN201611014616A CN106519182A CN 106519182 A CN106519182 A CN 106519182A CN 201611014616 A CN201611014616 A CN 201611014616A CN 106519182 A CN106519182 A CN 106519182A
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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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
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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
- C08G18/28—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
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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Abstract
The invention discloses an organic silicon modified polyurethane acrylate oligomer, and a preparation method thereof. The organic silicon modified polyurethane acrylate oligomer can be cured via radiation curing, and can be used in the field of special release coating. According to the preparation method, an organic silicon polyhydric alcohol is reacted with a diisocyanate compound, and blocking reaction with a hydroxied acrylate is carried out so as to obtain the organic silicon modified polyurethane acrylate oligomer. The preparation method is high in operability; synthesis method is simple; and preparation efficiency is high.
Description
Technical field
The present invention relates to a kind of macromolecule modified oligomer, for release coatings art, and in particular to a kind of machine Si modification
Urethane acrylate oligomer and preparation method.
Background technology
Electron beam（EB）Curing technology is described as the green skill of two Pius XIs circle as a kind of special radiation curing technology
Art, it has a no initiator, and curing rate is fast, low VOC, the advantages of discharge capacity is low, adhesive force is strong, just gradually replace
Traditional conventional coating techniques, are applied to the fields such as packaging for foodstuff, industrial gummed tape, release coating.In general, EB formulation for coating material
Generally comprise following components：Oligomer, monomer, auxiliary agent etc..
Oligomer is one of chief component of EB curing formulas, determines the performance of cured film.It is business-like
Oligomeric species are various, different according to its structure, can be divided into epoxy acrylate, urethane acrylate, polyester acrylic
Ester, polyether acrylate, amino acrylates etc..Under normal circumstances, these materials do not possess release function.
Organosilicon determines which as the had extremely low surface tension of separated type material because of its architectural characteristic, and fabulous is hydrophobic
Property, certain oleophobic property, superior wearability, weatherability etc.；But, traditional organic silicon modified polyurethane, adopt straight chain line more
Property organosilicon, its release effect are poor.Therefore, necessary on the basis of prior art, a kind of branched chain type of R ＆ D design has
Machine silicon modified polyurethane acrylate oligomer.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of machine silicon modified polyurethane third
Olefin(e) acid ester oligomer and preparation method, improve electron beam（EB）The release effect of curing process separated type material, improves product
Quality, reduce production cost.
To reach above-mentioned purpose, the technical solution used in the present invention is：A kind of organic silicon modified polyurethane acrylate is low
Polymers, it has below formula：
Wherein R1 is side chain type organosilicon dihydroxylic alcohols；X is CH3 or H；R2 is diisocyanate.
Preferably, the structural formula of the R1 is
。
Preferably, above-described organic silicon modified polyurethane acrylate oligomer, described R2 are toluene
Diisocyanate, hexamethylene diisocyanate or IPDI.
The preparation method of the organic silicon modified polyurethane acrylate oligomer that the present invention is provided, which comprises the following steps：
(1) organosilicon dihydroxylic alcohols is well mixed with diisocyanate, makes hydroxyl be 1 with the mol ratio of isocyano：2, it is added dropwise
Catalyst, is warmed up to 60 ~ 70 DEG C, is incubated 1 ~ 3h, and reaction prepolymer is standby；
(2) by hydroxy-ethyl acrylate or hydroxyethyl methacrylate, polymerization inhibitor is added to the prepolymer that step (1) is prepared
In, make hydroxyl be 1 with the mol ratio of isocyano：1, it is to slowly warm up to 80 ~ 90 DEG C and is incubated 2 ~ 3 hours, then uses infrared spectrum
Isocyano signal in detection reaction system, until isocyanato infrared signal disappears stops insulation, obtains organosilicon and changes
Property urethane acrylate oligomer.
Preferably, the preparation method of above-described organic silicon modified polyurethane acrylate oligomer, described
Catalyst be dibutyl tin laurate.
Preferably, the preparation method of above-described organic silicon modified polyurethane acrylate oligomer, described
Polymerization inhibitor be MEHQ.
Preferably, the preparation method of above-described organic silicon modified polyurethane acrylate oligomer, described
The step of (1) reaction temperature be 60 DEG C, temperature retention time is 2h.
Preferably, the preparation method of above-described organic silicon modified polyurethane acrylate oligomer, which is special
Levy and be, described step (2) reaction temperature is 80 DEG C, and temperature retention time is 3h.
Due to the utilization of above-mentioned technical proposal, the present invention has following advantages compared with prior art：
1st, the urethane acrylate oligomer that the present invention is provided, radiation-hardenable, especially surface tension is low, wherein adopt
Branched chain type organosilicon polyol masses, which has good release effect, branched chain type organosilicon is introduced double bond, in radiation condition
Curable is crosslinked, and can be used for special protection coatings art, prepares release coating.
2nd, the preparation method of the urethane acrylate oligomer that the present invention is provided, using organosilicon polyalcohol and two isocyanides
Ester compound reacts, and then Jing hydroxy acrylates are blocked again, obtain urethane acrylate, whole process operability
By force, synthetic reaction is simple, it is easy to control, and the urethane acrylate oligomer for preparing can overcome conventional polyurethanes propylene
Acid esters oligomer can not be release defect.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
1st, the preparation of organic silicon modified polyurethane acrylate oligomer
(1) in equipped with reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles add 320g organosilicons polynary
Alcohol X-22-176DX, is subsequently adding 44.2g IPDIs, two drop dibutyl tin laurates（DBTDL）Catalysis
Agent, be stirred at room temperature it is uniform after it is slow heat up, in 75 DEG C of insulation reactions 2 hours, then determine isocyano-content, if content does not have
Initial concentration half is reduced to, then continues insulation, till measured value is initial value half, reaction obtains polyurethane prepolymer
Thing, it is standby.
(2) polyurethane prepolymer that 23.2g hydroxy-ethyl acrylates, 0.25g MEHQs addition step (1) are obtained
Thing, is to slowly warm up to 80 DEG C and is incubated 3 hours, then infrared spectrum detection isocyano signal, until the group blackout stops
Only it is incubated, after the completion of reaction, obtains organic silicon modified polyurethane acrylate oligomer.
Embodiment 2
1st, the preparation of organic silicon modified polyurethane acrylate oligomer
(1) the addition 320g organosilicon polyalcohols in equipped with reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles
X-22-176DX, 44.2g IPDI, two drop DBTDL catalyst are stirred at room temperature uniform rear slow intensification,
75 DEG C of insulation 3h, then determine isocyano-content.If content is not lowered to initial concentration half, continue insulation, directly
To measured value is initial value half.Above-mentioned steps complete to obtain polyurethane prepolymer.
(2) 26.6g hydroxyethyl methacrylates, 0.25g MEHQs are added into prepolymer, is to slowly warm up to 80 DEG C
Insulation 3 hours, then infrared spectrum detection isocyano signal, stops insulation up to the group blackout.After the completion of reaction
Organic silicon modified polyurethane acrylate oligomer is obtained.
Embodiment 3
1st, the preparation of organic silicon modified polyurethane acrylate oligomer
(1) in equipped with reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles add 320g organosilicons polynary
Alcohol X-22-176DX, 44.6g toluene di-isocyanate(TDI), two drop DBTDL catalyst are stirred at room temperature uniform rear slow intensification, 70
DEG C insulation 2h, then determine isocyano-content.If content is not lowered to initial concentration half, continue insulation, until
Till measured value is initial value half.Above-mentioned steps complete to obtain polyurethane prepolymer.
(2) 23.2g hydroxy-ethyl acrylates, 0.25g MEHQs are added into prepolymer, is to slowly warm up to 90 DEG C of insulations
2 hours, then infrared spectrum detection isocyano signal, stopped insulation up to the group blackout.Obtain final product after the completion of reaction
To organic silicon modified polyurethane acrylate oligomer.
Embodiment 4
1st, the preparation of organic silicon modified polyurethane acrylate oligomer
(1) in equipped with reflux condensing tube, drying tube and churned mechanically 500 mL three-necked bottles add 320g organosilicons polynary
Alcohol X-22-176DX, 33.6g hexamethylene diisocyanate, two drop DBTDL catalyst are stirred at room temperature uniform rear slow intensification,
2h is incubated in 70 oC, isocyano-content is then determined.If content is not lowered to initial concentration half, continue insulation,
Till measured value is initial value half.Above-mentioned steps complete to obtain polyurethane prepolymer.
(2) 23.2g hydroxy-ethyl acrylates, 0.25g MEHQs are added into prepolymer, is to slowly warm up to 90 oC guarantors
Temperature 2 hours, then infrared spectrum detection isocyano signal, stops insulation up to the group blackout.After the completion of reaction i.e.
Obtain organic silicon modified polyurethane acrylate oligomer.
Embodiment 5
Filled a prescription according to table 1 with the urethane acrylate oligomer prepared in embodiment 1 respectively, prepare a series of compositions.Point
Be not well mixed which said composition stirring, 200 microns of thick films are painted with spreader on tinplate, use the U.S.
（Fusion UV Systems companies）Sample is placed in 10 centimetres of lamps away from place, finally by the medium pressure mercury lamp F300S-6 irradiation of production
Obtain the solidify coating of hard transparent.Its curing membrane performance testing result is as shown in table 1.
The composite formula and performance test results of 1 urethane acrylate oligomer of table
※
※ CN120：The epoxy acrylate of U.S.'s Sartomer Company production.
※ SR351：The trimethylolpropane trimethacrylate of U.S.'s Sartomer Company production.
※ SR238：1, the 6- hexanediyl esters of U.S.'s Sartomer Company production.
※ Irgacure 1173：The light trigger of BASF Corp. of Germany's production.
The urethane acrylate oligomer prepared in the embodiment of the present invention 1 is can be seen that from the test result of table 1
With good hydrophobicity.But with the increase of addition, its compatibility is gradually deteriorated, cured film pliability increases.
Embodiment 6
With embodiment 1, embodiment 2, embodiment 3, the urethane acrylate oligomer prepared in embodiment 4 is respectively according to table 2
Formula, prepares a series of compositions.It is well mixed which said composition stirring respectively, is painted with spreader on tinplate
200 microns of thick films, use the U.S.（Fusion UV Systems companies）The medium pressure mercury lamp F300S-6 irradiation of production, by sample
10 centimetres of lamps are placed in away from place, the solidify coating of hard transparent is finally obtained.Its curing membrane performance testing result is as shown in table 2.
The composite formula and performance test results of 2 urethane acrylate oligomer of table
※
※ Corning6008：The urethane acrylate of German Kening Co., Ltd's production.
※ 611B-85：The urethane acrylate of Taiwan Changxing company production.
※ EM235：The pentaerythritol triacrylate of Taiwan Changxing company production.
※ EM223：The tri (propylene glycol) diacrylate of Taiwan Changxing company production.
※ Irgacure 1173：The light trigger of BASF Corp. of Germany's production.
Composition 5,6,7,8 be can be seen that in outward appearance from the test result of table 2, hardness, flexibility are essentially identical,
But water contact angle slightly has difference.Wherein, the water contact angle of composition 8 is maximum, and this may be related to the structure of HDI.HDI has two
Individual activity identical isocyanate groups substantially, easily produce chain extending reaction in synthesis, cause molecular weight of product to increase, so as to
The transport efficiency of organosilicon is improved, contact angle is ultimately resulted in bigger than normal.The polyurethane propylene prepared in hindering the embodiment of the present invention 1
Acid esters has good hydrophobicity.But with the increase of addition, its compatibility is gradually deteriorated, cured film water contact angle increases.
Embodiment 7
Filled a prescription according to table 3 with the urethane acrylate oligomer prepared in embodiment 4 respectively, prepare composition.Respectively should
Composition stirring is well mixed which, paints 100 microns of thick films with spreader, use EB curing apparatus on cardboard
XXXXXXXXXXXXX, accelerating potential XXXXXX, electric current XXXXXXX, dosage is XXXXXXXXXXXXX, radiation mode
XXXXXXXXXXXXX, finally obtains the solidify coating of hard transparent.Its curing membrane performance testing result is as shown in table 3.
The composite formula and performance test results of 3 urethane acrylate oligomer of table
※
※ EB264：The urethane acrylate of Zhan Xin Resins Corporations production.
※ CN965：The urethane acrylate of U.S.'s Sartomer Company production.
※ CN104：The epoxy acrylate of U.S.'s Sartomer Company production.
※ EM231：The trimethylolpropane trimethacrylate of Taiwan Changxing company production.
※ EM223：The tri (propylene glycol) diacrylate of Taiwan Changxing company production.
※ SR335:The lauryl alcohol ester of U.S.'s Sartomer Company production.
Composition 9 be can be seen that with outstanding hydrophobicity from the test result of table 3
The above is only the concrete application example of the present invention, protection scope of the present invention is not limited in any way.It is all to adopt equivalent
Conversion or equivalence replacement and the technical scheme that formed, all fall within rights protection scope of the present invention.
Claims (8)
1. a kind of machine silicon modified polyurethane acrylate oligomer, it is characterised in that with below formula：
Wherein R1 is side chain type organosilicon dihydroxylic alcohols；
X is CH3 or H；R2 is diisocyanate.
2. machine silicon modified polyurethane acrylate oligomer according to claim 1, it is characterised in that：The R2 is toluene
Diisocyanate, hexamethylene diisocyanate or IPDI.
3. machine silicon modified polyurethane acrylate oligomer according to claim 1, it is characterised in that：The structure of the R1
Formula is
。
4. a kind of preparation method of machine silicon modified polyurethane acrylate oligomer, it is characterised in that：Characterized in that, including with
Lower step：
(1) organosilicon dihydroxylic alcohols is well mixed with diisocyanate, makes hydroxyl be 1 with the mol ratio of isocyano：2, it is added dropwise
Catalyst, is warmed up to 60～70 DEG C, is incubated 1～3h, and reaction prepolymer is standby；
(2) hydroxy-ethyl acrylate or hydroxyethyl methacrylate, polymerization inhibitor are added to into the prepolymer that step (1) is prepared
In, make hydroxyl be 1 with the mol ratio of isocyano：1；It is to slowly warm up to 80～90 DEG C and is incubated 2～3 hours, then uses infrared light
Isocyano signal in spectrum detection reaction system, until isocyanato infrared signal disappears stops insulation, obtains organosilicon
Modified urethane acrylate oligomer.
5. the preparation method of machine silicon modified polyurethane acrylate oligomer according to claim 4, it is characterised in that：Institute
The catalyst stated is dibutyl tin laurate.
6. the preparation method of organic silicon modified polyurethane acrylate oligomer according to claim 4, it is characterised in that：
Described polymerization inhibitor is MEHQ.
7. the preparation method of machine silicon modified polyurethane acrylate oligomer according to claim 4, it is characterised in that：Institute
The step of stating (1) reaction temperature is 60 DEG C, and temperature retention time is 2h.
8. the preparation method of organic silicon modified polyurethane acrylate oligomer according to claim 4, it is characterised in that：
Described step (2) reaction temperature is 80 DEG C, and temperature retention time is 3h.
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Cited By (9)
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|---|---|---|---|---|
| CN108165087A (en) * | 2017-12-28 | 2018-06-15 | 中科院广州化学有限公司 | A kind of anti-anodic oxidation protection ink and preparation method and application |
| CN109577077A (en) * | 2018-12-07 | 2019-04-05 | 烟台博源科技材料股份有限公司 | Electronic beam curing adhesive sticker release paper and preparation method thereof |
| CN109762461A (en) * | 2019-01-29 | 2019-05-17 | 湖南邦弗特新材料技术有限公司 | A kind of super abrasive anti-pollution UV is coating material solidified and its preparation method and application |
| CN110452361A (en) * | 2019-07-09 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | A kind of synthetic method and waterproofing agent of the polyurethane acroleic acid modified organic silicon without fluoro water proofing agent |
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| CN114605646A (en) * | 2022-03-31 | 2022-06-10 | 四川大学 | Thermosetting polyurethane modified polysiloxane material capable of being repeatedly processed and used and preparation method thereof |
| WO2022152775A1 (en) | 2021-01-15 | 2022-07-21 | Evonik Operations Gmbh | Silicone urethane (meth)acrylates and their use in 3d printing resins and coating compositions |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187827A (en) * | 1995-06-14 | 1998-07-15 | 诺瓦提斯公司 | Polymerizable siloxane macromonomers |
| CN101094879A (en) * | 2004-12-29 | 2007-12-26 | 博士伦公司 | Polysiloxane prepolymers for biomedical devices |
| CN104125969A (en) * | 2012-02-15 | 2014-10-29 | 帝斯曼知识产权资产管理有限公司 | Polysiloxane based block copolymers |
-
2016
- 2016-11-18 CN CN201611014616.XA patent/CN106519182A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187827A (en) * | 1995-06-14 | 1998-07-15 | 诺瓦提斯公司 | Polymerizable siloxane macromonomers |
| CN101094879A (en) * | 2004-12-29 | 2007-12-26 | 博士伦公司 | Polysiloxane prepolymers for biomedical devices |
| CN104125969A (en) * | 2012-02-15 | 2014-10-29 | 帝斯曼知识产权资产管理有限公司 | Polysiloxane based block copolymers |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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