CN106977686B - A kind of urethane acrylate copolymer and preparation method thereof containing poly- fluorosilicone block - Google Patents
A kind of urethane acrylate copolymer and preparation method thereof containing poly- fluorosilicone block Download PDFInfo
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- CN106977686B CN106977686B CN201710181270.0A CN201710181270A CN106977686B CN 106977686 B CN106977686 B CN 106977686B CN 201710181270 A CN201710181270 A CN 201710181270A CN 106977686 B CN106977686 B CN 106977686B
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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
- C08G18/67—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
- C08G18/28—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of urethane acrylate copolymer containing poly- fluorosilicone block, which has the structural formula as shown in formula i:Or
Description
Technical field
The present invention relates to a kind of urethane acrylate, in particular to a kind of polyurethane propylene containing poly- fluorosilicone block
Acid ester copolymer and preparation method thereof.
Background technique
Applied to plastic materials such as PC, PMMA, PET in building trade, carrier, 3C industry, may require that with one
Fixed hardness, abrasion resistance, water resistance, antifouling property etc..Generally by coating stiffened coating processing, thus assign it is special
Function reaches application requirement.
There is good hydrophobic, oleophobic, anti-pollution, wear-resisting, stiffened after capable of achieving the effect that overlay film, solution so far is
In coating, realized by addition fluorine auxiliary agent.In the raw material of coating, common polyurethane acrylic resin is only capable of being given to
There is stiffened and certain wear-resisting property after film, can not fully meet.And after being added to fluorine auxiliary agent in coating, then it can be given to
There are high water contact angle (100 ° -108 °) after film, good wear-resisting property (steel wool abrasion-resistant testing time 50-200 bout).
But fluorine auxiliary agent is at high cost, and with Miscibility is poor, stability is poor, and be easy to cause various in coating or application process
Limitation, is often not achieved best ideal effect.
As the high quality of development in science and technology and people are pursued, need to develop a kind of polyurethane acrylic resin, in coating
Compatibility is good in system, good stability, and cost is relatively low, and is able to satisfy and has to after the plastic materials overlay film such as PC, PMMA, PET
Excellent hydrophobic, oleophobic, anti-pollution, wear-resisting, stiffened effect.
Summary of the invention
In order to overcome the disadvantages and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of dredging with improvement
Water, oleophobic and antifouling property, and urethane acrylate copolymer of the improved wear-resisting property containing poly- fluorosilicone block.
It is a further object of the present invention to provide the systems of the above-mentioned urethane acrylate copolymer containing poly- fluorosilicone block
Preparation Method.
The present invention is achieved through the following technical solutions:
A kind of urethane acrylate copolymer containing poly- fluorosilicone block, which has ties as shown in formula i
Structure formula:
Wherein, formula i be by reactant A, B, C as obtained by addition reaction；
Wherein, R is the oligomeric fluorosilicone from reactant A,
R ' is the diisocyanate from reactant B,
R " is the alkyl acrylate from reactant C；
The value range of m is 1-100, preferably 10-50.
When the value range of m is greater than 100, the degree of polymerization is high, causes viscosity big, and operation is difficult.
Wherein, the reactant A has the structural formula as shown in formula ii:
Wherein, the value range of n is 1-100, preferably 5-50.
When the value range of n is greater than 100, the degree of polymerization is high, causes viscosity big, and operation is difficult, and is unfavorable for reacting.
Wherein, the viscosity of the reactant A is 0.005-100Pas.The viscosity is to fly viscosimeter 25 using rich strangle
Test obtains after DEG C constant temperature 2 hours or more.
Wherein, the reactant B is diisocyanate, is selected from isophorone diisocyanate IPDI, diphenyl methane two
Isocyanates MDI, 4,4'- dicyclohexyl methyl hydride diisocyanate HMDI, hexamethylene diisocyanate HDI, toluene diisocyanate
One or more of acid esters TDI.
Wherein, the reactant C is selected from hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, second
Aoxidize trimethylolpropane trimethacrylate, pentaerythritol triacrylate, one of Dipentaerythritol Pentaacrylate or
It is several.
The invention also discloses a kind of preparation sides of above-mentioned urethane acrylate copolymer containing poly- fluorosilicone block
Method includes the following steps:
1) it prepares reactant A: by trifluoro propyl methyl cyclotrisiloxane by acid catalysis, being reacted at 50-90 DEG C, after pumping is low
Obtain reactant A；
2) preparation NCO group blocks
Block presoma: being down to 15-35 DEG C after reactant A is vacuumized 1-2 hours at 110-120 DEG C, with reactant B in 50-70
It is reacted 2-4 hours at DEG C, obtains NCO group sealing end
Block presoma；
3) it is down to 15-35 DEG C after vacuumizing reactant C at 110-120 DEG C 1-2 hours, with NCO group sealing end
Block presoma reacted at 70-90 DEG C 3-6 hours to get.
Wherein, in step 1), the acid catalysis refers to using resin cation as acid catalyst；It is described take out low finger will be low
Boiler material is extracted out by negative pressure.
Wherein, in step 2), the molar ratio of the reactant A and reactant B is 1:1-2.
Wherein, in step 3), the reactant C and NCO group sealing end
The molar ratio of block presoma is 1-2:1.
Compared with prior art, the present invention having the following beneficial effects:
Urethane acrylate copolymer containing poly- fluorosilicone block of the invention, due to introducing specific molecular chain (m=
Poly- fluorosilicone block 1-100) can make copolymer acquisition be difficult to expect performance improvement, hydrophobic, thin including improvement
Oil and antifouling property, and improved wear-resisting property.Especially by after copolymer application film forming, can mention in application process
The compatibility and stability of high whole system, to equally also have good hydrophobic, antifouling property, and improved wearability
Energy.
Specific embodiment
Further illustrate that the present invention, following embodiment are the preferable embodiment party of the present invention below by specific embodiment
Formula, but embodiments of the present invention are not limited by following embodiments.
The embodiment of the present invention and comparative example use trifluoro propyl methyl cyclotrisiloxane, IPDI, MDI, methacrylic acid
Hydroxyl ethyl ester, hydroxy propyl methacrylate are all from commercially available.
The testing standard or method of each performance:
Polymerization degree n: GPC and nuclear-magnetism；
Viscosity: rich strangle flies viscosimeter；
Hydrophobicity: water contact angle；
Pollution resistance: oiliness stroke write state, and easily wipe degree；
Wearability: steel wool wear-resisting test, linear wear instrument, steel wool are U.S. HOMAX#0000, pressure 1000g/
cm2, stroke 3.3cm, speed 40cycles/min.
The preparation of reactant A
It by trifluoro propyl methyl cyclotrisiloxane by acid catalysis, reacts, is obtained after pumping is low as shown in table 1 at 50-90 DEG C
The reactant A of the degree of polymerization and viscosity；
The data of 1 reactant A of table
Embodiment 1-10 and comparative example 1: the preparation of the urethane acrylate copolymer containing poly- fluorosilicone block
It is down to 15-35 DEG C after the reactant A that table 1 is prepared is vacuumized 1-2 hours at 110-120 DEG C, and is reacted
Object B reacts 2-4 hours at 50-70 DEG C, obtains NCO group sealing end
Block presoma；Then it is down to 15-35 DEG C after reactant C being vacuumized 1-2 hours at 110-120 DEG C again, is sealed with NCO group
End
Block presoma reacts 3-6 hours at 70-90 DEG C to get the urethane acrylate copolymer containing poly- fluorosilicone block.
The urethane acrylate copolymer containing poly- fluorosilicone block being prepared is matched according to table 2
System solidifies to form a film by ultraviolet light；The test knot of the indexs such as hydrophobicity, pollution resistance and the wearability of preparation gained film
Fruit is as shown in table 3.
The preparation gained film reference formulation of table 2
| Name of material | Dosage (g) |
| Urethane acrylate copolymer containing poly- fluorosilicone block | 53.75 |
| IRGACURE184 | 2.69 |
| TEGO RAD2100 | 0.05 |
| Methyl iso-butyl ketone (MIBK) | 43.51 |
| TOTAL | 100.00 |
3 embodiment 1-10 of table and the synthon of comparative example 1 are with when each testing performance index result
From the embodiment 1-10 of table 3 and the comparison of comparative example 1 it can be seen that of the invention poly- containing poly- fluorosilicone block
Urethane acrylate copolymer answers the copolymer due to introducing the poly- fluorosilicone block of specific molecular chain (m=1-100)
After film forming, the compatibility and stability of whole system can be improved in application process, to equally also have good dredge
Water, oleophobic, antifouling property, and improved wear-resisting property.And when the polyurethane-acrylic emulsion copolymerization for containing poly- fluorosilicone block
The m value of object is greater than 100, and as shown in comparative example 1, the hydrophobicity of the film, oleophobic property, pollution resistance and wearability are poor.
Claims (7)
1. a kind of urethane acrylate copolymer containing poly- fluorosilicone block, which is characterized in that the copolymer is by reacting
Object A, B, C have the structural formula as shown in formula i as obtained by addition reaction:
Or
In formula I, R is the oligomeric fluorosilicone residue from reactant A, and R' is the diisocyanate residue from reactant B,
R " is the alkyl acrylate residue from reactant C, and the value range of m is 1-100；
The reactant A has the structural formula as shown in formula II:
In formula II, the value range of n is 1-100.
2. a kind of urethane acrylate copolymer containing poly- fluorosilicone block according to claim 1, feature exist
In the viscosity of the reactant A is 0.005-100Pas.
3. a kind of urethane acrylate copolymer containing poly- fluorosilicone block according to claim 1, feature exist
In the reactant B is selected from isophorone diisocyanate IPDI, methyl diphenylene diisocyanate MDI, 4,4'-, bis- hexamethylene
One or more of dicyclohexylmethane diisocyanate HMDI, hexamethylene diisocyanate HDI, toluene di-isocyanate(TDI) TDI.
4. a kind of urethane acrylate copolymer containing poly- fluorosilicone block according to claim 1, feature exist
In the reactant C is selected from hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, pentaerythrite 3 third
One or more of olefin(e) acid ester, Dipentaerythritol Pentaacrylate.
5. a kind of preparation method of the urethane acrylate copolymer as described in claim 1 containing poly- fluorosilicone block,
Include the following steps:
1) it prepares reactant A: by trifluoro propyl methyl cyclotrisiloxane by acid catalysis, reacting at 50-90 DEG C, obtained after pumping is low
Reactant A, the pumping is low to be referred to low boiling material, is extracted out by negative pressure；
2) preparation NCO group blocks
Or
Block presoma: it is down to 15-35 DEG C after reactant A is vacuumized 1-2 hours at 110-120 DEG C, is existed with reactant B
It is reacted 2-4 hours at 50-70 DEG C, obtains NCO group sealing end
Or
Block presoma；
3) it is down to 15-35 DEG C after vacuumizing reactant C at 110-120 DEG C 1-2 hours, with NCO group sealing end
Or
Block presoma reacted at 70-90 DEG C 3-6 hours to get.
6. the preparation method of the urethane acrylate copolymer according to claim 5 containing poly- fluorosilicone block,
It is characterized in that, in step 2), the molar ratio of the reactant A and reactant B is 1:1-2.
7. the preparation method of the urethane acrylate copolymer according to claim 5 containing poly- fluorosilicone block,
It is characterized in that, in step 3), the reactant C and NCO group sealing end
Or
The molar ratio of block presoma is 1-2:1.
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| CN109763337B (en) * | 2018-12-18 | 2021-09-10 | 上海华峰超纤科技股份有限公司 | Waterproof and breathable superfine fiber suede leather and preparation method and application thereof |
| CN109705310B (en) * | 2018-12-18 | 2021-09-10 | 上海华峰超纤科技股份有限公司 | Polyurethane resin for waterproof breathable leather and preparation method thereof |
| CN116102969A (en) * | 2022-09-07 | 2023-05-12 | 江苏斯迪克新材料科技股份有限公司 | Fingerprint-resistant UV (ultraviolet) curing coating for film, preparation method of fingerprint-resistant UV curing coating and preparation method of film |
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