CN110183670A - A kind of bipolarity dissaving polymer UV matt process for preparing resins and the resin - Google Patents
A kind of bipolarity dissaving polymer UV matt process for preparing resins and the resin Download PDFInfo
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- CN110183670A CN110183670A CN201910482400.3A CN201910482400A CN110183670A CN 110183670 A CN110183670 A CN 110183670A CN 201910482400 A CN201910482400 A CN 201910482400A CN 110183670 A CN110183670 A CN 110183670A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
Abstract
The invention discloses a kind of bipolarity dissaving polymer UV matt process for preparing resins and the resins, end carboxyl super branched polyester is prepared using dihydromethyl propionic acid, by the modified acquisition hydroxyl hyper-branched polyester UV resin of (methyl) glycidyl acrylate (ether), so that end is linked siloxane molecule segment by Si―H addition reaction is modified later, obtains hydroxyl bipolarity dissaving polymer UV matt resin.This UV resin is one-component structural, the dissaving polymer segment there are two types of different structure is contained in resin structure, one is polysiloxanes nonpolarity segments, and one is the polyester polarity segments containing hydroxyl.Polysiloxanes segment self-constriction during photocuring of the UV resin of this structure forms the exposed nanoscale microballoon of siloxanes segment, is embedded in the space three-dimensional network structure that hyper-branched polyester is formed, plays matt effect.
Description
Technical field
The present invention relates to UV solidified resins to synthesize field technical field, more particularly, to a kind of bipolarity hyperbranched poly
Close object UV matt process for preparing resins and the resin.
Background technique
With the upgrading of social industrial level and people's level of consumption, consumer is outer to articles for daily use and industrial goods
Sight, sense of touch, experience comfort level require increasingly harshness.Many top grade articles start to inhale with beautiful, comfortable shape and sense of touch
Draw public attention.The application of matt coating is also just come into being.It is with beautiful appearance, comfortable Human physiology sense of touch,
It gradually gains a place in industries such as automobile interior decoration, electronic products, and increasingly obtains more favors.UV photocuring technology by
, VOC free discharge environmentally protective in its, low power consuming solidify the advantages that quick, become the following green coating with development potential
Material new technology.
The preparation that UV solidifies matt coating material at present relies primarily on addition inorganic filler, i.e., is added into the system of coating
A certain amount of delustring auxiliary agent, silica or aluminum oxide of predominantly various partial sizes etc., these fillers can pass through delustring
Effect reaches matt effect.But the organic system of the inorganic filler of addition and coating is difficult perfection and dissolves each other, it is long-term to place necessarily
Appearance such as separates at the unstable states, in the storage in later period and in use, being located at since the sedimentation of filler may cause inorganic filler
Container bottom, influences the Painting effect in later period, causes adverse effect to production.
For problem noted earlier, there is an urgent need to one kind not to add inorganic flatting silica in the market, included matt effect itself
UV solidified resin.
Summary of the invention
In view of the above problems, the invention proposes a kind of bipolarity dissaving polymer UV matt process for preparing resins and should
Resin, this UV resin are one-component structurals, and the dissaving polymer segment there are two types of different structure is contained in resin structure, one is
Polysiloxanes nonpolarity segment, one is the polyester polarity segments containing hydroxyl.Mistake of the UV resin of this structure in photocuring
The self-constriction of polysiloxanes segment forms the exposed nanoscale microballoon of siloxanes segment, the space that insertion hyper-branched polyester is formed in journey
In three-dimensional net structure, matt effect is played.
The present invention provides a kind of bipolarity dissaving polymer UV matt process for preparing resins, includes the following steps:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously: vinyl three is prepared using the following raw material
Chlorosilane,
Chlorodimethyl silane,
Ether and water；
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid,
First catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or metering system
Any one of acid glycidyl ether；
Step c: the end group silicone active body containing double bond and si-h bond simultaneously is catalyzed using the second catalyst
And hydroxyl hyper-branched polyester.
Further, the end group silicone active body containing double bond and si-h bond simultaneously, hydroxyl hyper-branched polyester
The mass parts of UV resin and the second catalyst are as follows:
0.1-20 parts of silicone active body simultaneously containing double bond and si-h bond of end group,
80-99.9 parts of UV resin of hydroxyl hyper-branched polyester,
Second 0.05-0.1 parts of catalyst.
Further, first catalyst is triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- diformazan basic ring
Hexylamine, N, N '-diethyl piperazine, N-ethylmorpholine pyridine and one or more of N or N '-dimethyl pyridine；
Second catalyst is that chloroplatinic acid or phosphine are coordinated one of rhodium complex.
Further, the preparation step of silicone active body of the end group simultaneously containing double bond and si-h bond includes:
Vinyl trichlorosilane, chlorodimethyl silane, ether and water are added in reaction kettle after weighing proportionally, T1 item
It is stirred n1 hours under part；
It is warming up to T2, it is organic containing double bond and si-h bond simultaneously that end group is made in decompression vacuum pumping water removal and solvent ether
Silicon active body.
Further, the preparation step of the hydroxyl hyper-branched polyester UV resin includes:
Dihydromethyl propionic acid is added in reaction kettle, and the first catalyst is added, and stirring is warming up to T3 in n2 hours, reacts n3
Hour, end carboxyl super branched polyester is made；
By glycidyl acrylate, glycidyl methacrylate, glycidyl ether or methacrylic acid
The reaction kettle that end carboxyl super branched polyester is made is added in any one of glycidol ether, and insulation reaction n4 is small at a temperature of T4
When, hydroxyl hyper-branched polyester UV resin is made.
Further, first catalyst is the 0.1%-2% of dihydromethyl propionic acid quality；The acrylic acid shrinks sweet
Any one of grease, glycidyl methacrylate, glycidyl ether or methyl propenoic acid glycidyl ether
Quality is the 10-35% of dihydromethyl propionic acid quality.
Further, the T1 is 30 DEG C of any temperature values in -50 DEG C of sections；The n1 is -6 hours 4 hours any durations；
The T2 is 100 DEG C of any temperature values in -150 DEG C of sections；The n2 is -1 hour 0 hour any duration；The T3 be 90 DEG C-
130 DEG C of any temperature values in section；The n3 is -8 hours 4 hours any durations；The T4 is 90 DEG C of any temperature in -130 DEG C of sections
Angle value；The n is -4 hours 2 hours any durations.
Further, following mass parts Material synthesis is utilized:
0.1-20 parts of silicone active body simultaneously containing double bond and si-h bond of end group；
80-99.9 parts of UV resin of hydroxyl hyper-branched polyester；
Any 0.05-0.1 parts in chloroplatinic acid or phosphine coordination rhodium complex.
Further, the end group silicone active containing double bond and si-h bond simultaneously is prepared using the raw material of following mass parts
Body:
2.8-3 parts of vinyl trichlorosilane,
43.7-45 parts of chlorodimethyl silane,
150-300 parts of ether,
10-15 parts of water；
Hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid,
Catalyst triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-diethyl piperazine
Piperazine, N-ethylmorpholine pyridine and one or more of N or N '-dimethyl pyridine；
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or metering system
Any one of acid glycidyl ether；
The catalyst is the 0.1%-2% of dihydromethyl propionic acid quality；The glycidyl acrylate, metering system
The quality of any one of acid glycidyl ester, glycidyl ether or methyl propenoic acid glycidyl ether is dihydroxymethyl
The 10-35% of propionic acid quality.
A kind of bipolarity dissaving polymer UV matt resin of the invention and the resin prepare end using dihydromethyl propionic acid
Carboxyl super branched polyester, by glycidyl acrylate, glycidyl methacrylate, glycidyl ether or first
Any modified acquisition hydroxyl hyper-branched polyester UV resin in base glycidyl ether passes through Si―H addition reaction later
It is modified that end is made to link siloxane molecule segment, obtain hydroxyl bipolarity dissaving polymer UV matt resin.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, below to the technology in the embodiment of the present invention
Scheme is clearly and completely described.
In some processes of description and claims of this specification description, contain according to particular order appearance
Multiple operations, but it should be clearly understood that these operations can not execute or parallel according to its sequence what appears in this article
It executes, the serial number of operation such as step a, step b etc. are only used for distinguishing each different operation, and serial number itself does not represent
Any executes sequence.In addition, these processes may include more or fewer operations, and these operations can be held in order
Capable or parallel execution.
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those skilled in the art
Member's every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
A kind of bipolarity dissaving polymer UV matt process for preparing resins, includes the following steps:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously: vinyl three is prepared using the following raw material
Chlorosilane,
Chlorodimethyl silane,
Ether and water；
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid,
First catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or metering system
Any one of acid glycidyl ether；
Step c: the end group silicone active body containing double bond and si-h bond simultaneously is catalyzed using the second catalyst
And hydroxyl hyper-branched polyester UV resin reaction.
UV solidification is ultra-violet curing, and UV is the english abbreviation of ultraviolet light, and solidification refers to that substance is changed into high score from low molecule
The process of son.UV solidifies coating (paint), ink, adhesive (glue) or the other fillings for generally referring to need with ultraviolet curing
Condition of cure or the requirement for sealing sealant, are different from heating cure, glue crosslinking agent (curing agent) solidification, spontaneous curing etc..
It is one-component structural using this UV resin, the dissaving polymer chain there are two types of different structure is contained in resin structure
Section, one is polysiloxanes nonpolarity segments, and one is the polyester polarity segments containing hydroxyl.The UV resin of this structure is in light
Polysiloxanes segment self-constriction forms the exposed nanoscale microballoon of siloxanes segment during cured, is embedded in hyper-branched polyester shape
At space three-dimensional network structure in, play matt effect.
The end group silicone active body containing double bond and si-h bond simultaneously, hydroxyl hyper-branched polyester UV resin and
The mass parts of second catalyst are as follows:
0.1-20 parts of silicone active body simultaneously containing double bond and si-h bond of end group,
80-99.9 parts of UV resin of hydroxyl hyper-branched polyester,
Second 0.05-0.1 parts of catalyst.
First catalyst be triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N,
N '-diethyl piperazine, N-ethylmorpholine pyridine and one or more of N or N '-dimethyl pyridine；
Second catalyst is that chloroplatinic acid or phosphine are coordinated one of rhodium complex.
The preparation step of silicone active body of the end group simultaneously containing double bond and si-h bond includes:
Vinyl trichlorosilane, chlorodimethyl silane, ether and water are added in reaction kettle after weighing proportionally, T1 item
It is stirred n1 hours under part；
It is warming up to T2, it is organic containing double bond and si-h bond simultaneously that end group is made in decompression vacuum pumping water removal and solvent ether
Silicon active body.
The mass parts of the vinyl trichlorosilane, chlorodimethyl silane, ether and water are as follows:
2.8-3 parts of vinyl trichlorosilane,
43.7-45 parts of chlorodimethyl silane,
150-300 parts of ether,
10-15 parts of water.
The preparation step of the hydroxyl hyper-branched polyester UV resin includes:
Dihydromethyl propionic acid is added in reaction kettle, and the first catalyst is added, and stirring is warming up to T3 in n2 hours, reacts n3
Hour, end carboxyl super branched polyester is made；
By glycidyl acrylate, glycidyl methacrylate, glycidyl ether or methacrylic acid
The reaction kettle that end carboxyl super branched polyester is made is added in any one of glycidol ether, and insulation reaction n4 is small at a temperature of T4
When, hydroxyl hyper-branched polyester UV resin is made.
First catalyst is the 0.1%-2% of dihydromethyl propionic acid quality；The glycidyl acrylate, methyl
The quality of any one of glycidyl acrylate, glycidyl ether or methyl propenoic acid glycidyl ether is dihydroxy
The 10-35% of methylpropanoic acid quality.
The T1 is 30 DEG C of any temperature values in -50 DEG C of sections；The n1 is -6 hours 4 hours any durations；The T2 is
100 DEG C of any temperature values in -150 DEG C of sections；The n2 is -1 hour 0 hour any duration；The T3 is 90 DEG C of -130 DEG C of sections
Any temperature value；The n3 is -8 hours 4 hours any durations；The T4 is 90 DEG C of any temperature values in -130 DEG C of sections；The n
For -4 hours 2 hours any durations.
Embodiment one:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously is prepared using the following raw material:
Vinyl trichlorosilane 2.8g, chlorodimethyl silane 45g, ether 150g and water 10g is weighed to be added in reaction kettle,
It is stirred 6 hours under the conditions of 30 DEG C；100 DEG C are warming up to, decompression vacuum pumping water removal and solvent ether, obtained end group contain double bond simultaneously
With the silicone active body of si-h bond.
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
It weighs dihydromethyl propionic acid 282g and triphenylphosphine 0.282g to be added in reaction kettle, stirring is warming up to 90 in 30 minutes
DEG C, it reacts 8 hours, end carboxyl super branched polyester is made；Glycidyl acrylate 28.2g is added, is kept the temperature at a temperature of 90 DEG C
Hydroxyl hyper-branched polyester UV resin is made in reaction 4 hours.
Step c: the end group silicone active body containing double bond and si-h bond simultaneously is catalyzed using the second catalyst
And hydroxyl hyper-branched polyester UV resin reaction, obtain bipolarity dissaving polymer UV matt resin:
Weigh end group in above-mentioned steps (1) the silicone active body 0.1g containing double bond and si-h bond simultaneously, above-mentioned step
Suddenly reaction kettle is added in hydroxyl hyper-branched polyester the UV resin 99.9g and chloroplatinic acid 0.05g in (2), and stirring is warming up to 30 DEG C,
Bipolarity dissaving polymer UV matt resin is made in reaction 6 hours.
Carrying out ultraviolet light curable to the bipolarity dissaving polymer UV matt resin of above-mentioned preparation can test, and take 20g
Resin is added 0.3g crack type photoinitiator 1- hydroxycyclohexyl phenyl ketone, is uniformly coated on the PET film table that sided corona treatment is crossed
Face, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light and apply
Layer, matt degree are 26.
Embodiment two:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously is prepared using the following raw material:
Vinyl trichlorosilane 3g, chlorodimethyl silane 43.7g, ether 300g and water 15g is weighed to be added in reaction kettle,
It is stirred 4 hours under the conditions of 50 DEG C；150 DEG C are warming up to, decompression vacuum pumping water removal and solvent ether, obtained hyperbranched polyorganosiloxane are living
Property body.
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
It weighs dihydromethyl propionic acid 300g and triethylamine 6g to be added in reaction kettle, stirring is warming up to 130 DEG C in 30 minutes, instead
It answers 4 hours, end carboxyl super branched polyester is made；Glycidyl methacrylate 105g is added, is kept the temperature at a temperature of 130 DEG C anti-
It answers 2 hours, hydroxyl hyper-branched polyester UV resin is made.
Step c: the end group silicone active body containing double bond and si-h bond simultaneously is catalyzed using the second catalyst
And hydroxyl hyper-branched polyester UV resin reaction, obtain bipolarity dissaving polymer UV matt resin:
Weigh end group in above-mentioned steps (1) the silicone active body 20g containing double bond and si-h bond simultaneously, above-mentioned steps
(2) reaction kettle is added in hydroxyl hyper-branched polyester UV resin 80g and chloroplatinic acid 0.1g in, and stirring is warming up to 50 DEG C, reaction 4
Hour, bipolarity dissaving polymer UV matt resin is made.
Carrying out ultraviolet light curable to the bipolarity dissaving polymer UV matt resin of above-mentioned preparation can test, and take 20g
Resin is added 0.3g crack type photoinitiator 1- hydroxycyclohexyl phenyl ketone, is uniformly coated on the PET film table that sided corona treatment is crossed
Face, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light and apply
Layer, matt degree are 12.
Embodiment three:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously is prepared using the following raw material:
It weighs vinyl trichlorosilane 3g, chlorodimethyl silane 45g, ether 300g and water 15g to be added in reaction kettle, 50
It is stirred 4 hours under the conditions of DEG C；150 DEG C are warming up to, decompression vacuum pumping water removal and solvent ether, obtained hyperbranched polyorganosiloxane are active
Body.
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid 286g and ammonium chloride 2.86g is weighed to be added in reaction kettle, stirring is warming up to 110 DEG C in 30 minutes,
Reaction 6 hours, is made end carboxyl super branched polyester；Glycidyl methacrylate 56g is added, is kept the temperature at a temperature of 110 DEG C
Hydroxyl hyper-branched polyester UV resin is made in reaction 3 hours.
Step c: the end group silicone active body containing double bond and si-h bond simultaneously is catalyzed using the second catalyst
And hydroxyl hyper-branched polyester UV resin reaction, obtain bipolarity dissaving polymer UV matt resin
Weigh end group in above-mentioned steps (1) the silicone active body 10g containing double bond and si-h bond simultaneously, above-mentioned steps
(2) reaction kettle is added in hydroxyl hyper-branched polyester UV resin 90g and chloroplatinic acid 0.08g in, and stirring is warming up to 40 DEG C, reaction 5
Hour, bipolarity dissaving polymer UV matt resin is made.
Carrying out ultraviolet light curable to the bipolarity dissaving polymer UV matt resin of above-mentioned preparation can test, and take 20g
Resin is added 0.3g crack type photoinitiator 1- hydroxycyclohexyl phenyl ketone, is uniformly coated on the PET film table that sided corona treatment is crossed
Face, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light and apply
Layer, matt degree are 19.
Example IV:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously is prepared using the following raw material:
It weighs vinyl trichlorosilane 2.8g, chlorodimethyl silane 43.7g, ether 150g and water 10g and reaction kettle is added
In, it is stirred 6 hours under the conditions of 30 DEG C；100 DEG C are warming up to, decompression vacuum pumping removes water and solvent ether, and hyperbranched poly silicon oxygen is made
Alkane active body.
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid 312g and N are weighed, N- dimethyl cyclohexyl amine 3.12g is added in reaction kettle, and stirring rises for 30 minutes
Temperature reacts 6 hours to 110 DEG C, end carboxyl super branched polyester is made；Methyl propenoic acid glycidyl ether 62.4g is added, 110
Hydroxyl hyper-branched polyester UV resin is made in insulation reaction 3 hours at a temperature of DEG C.
Step c: the end group silicone active body containing double bond and si-h bond simultaneously is catalyzed using the second catalyst
And hydroxyl hyper-branched polyester UV resin reaction, obtain bipolarity dissaving polymer UV matt resin:
Weigh end group in above-mentioned steps (1) the silicone active body 0.1g containing double bond and si-h bond simultaneously, above-mentioned step
Suddenly reaction kettle is added in the hydroxyl hyper-branched polyester UV resin 99.9g in (2) and phosphine coordination rhodium complex 0.05g, stirs, heating
It to 30 DEG C, reacts 6 hours, bipolarity dissaving polymer UV matt resin is made.
Carrying out ultraviolet light curable to the bipolarity dissaving polymer UV matt resin of above-mentioned preparation can test, and take 20g
Resin is added 0.3g crack type photoinitiator 1- hydroxycyclohexyl phenyl ketone, is uniformly coated on the PET film table that sided corona treatment is crossed
Face, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light and apply
Layer, matt degree are 14.
Embodiment five:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously is prepared using the following raw material:
Vinyl trichlorosilane 2.9g, chlorodimethyl silane 44g, ether 200g and water 12g is weighed to be added in reaction kettle,
It is stirred 5 hours under the conditions of 40 DEG C；120 DEG C are warming up to, decompression vacuum pumping water removal and solvent ether, obtained hyperbranched polyorganosiloxane are living
Property body.
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid 286g and N are weighed, N '-diethyl piperazine 2.8g is added in reaction kettle, stirring, heats up within 30 minutes
To 110 DEG C, reacts 6 hours, end carboxyl super branched polyester is made；Methyl propenoic acid glycidyl ether 56g is added, in 110 DEG C of temperature
Lower insulation reaction 3 hours are spent, obtained hydroxyl hyper-branched polyester UV resin.
Step c: the end group silicone active body containing double bond and si-h bond simultaneously is catalyzed using the second catalyst
And hydroxyl hyper-branched polyester UV resin reaction, obtain bipolarity dissaving polymer UV matt resin:
Weigh end group in above-mentioned steps (1) the silicone active body 20g containing double bond and si-h bond simultaneously, above-mentioned steps
(2) reaction kettle is added in hydroxyl hyper-branched polyester UV resin 80g and phosphine coordination rhodium complex 0.1g in, and stirring is warming up to 50
DEG C, it reacts 4 hours, bipolarity dissaving polymer UV matt resin is made.
Carrying out ultraviolet light curable to the bipolarity dissaving polymer UV matt resin of above-mentioned preparation can test, and take 20g
Resin is added 0.3g crack type photoinitiator 1- hydroxycyclohexyl phenyl ketone, is uniformly coated on the PET film table that sided corona treatment is crossed
Face, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light and apply
Layer, matt degree are 10.
Embodiment six:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously is prepared using the following raw material:
Vinyl trichlorosilane 2.9g, chlorodimethyl silane 44g, ether 210g and water 13g is weighed to be added in reaction kettle,
It is stirred 5 hours under the conditions of 40 DEG C；140 DEG C are warming up to, decompression vacuum pumping water removal and solvent ether, obtained hyperbranched polyorganosiloxane are living
Property body.
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
It weighs dihydromethyl propionic acid 282g and N-ethylmorpholine pyridine 0.282g to be added in reaction kettle, stirring rises for 30 minutes
Temperature reacts 8 hours to 90 DEG C, end carboxyl super branched polyester is made；Glycidyl ether 28.2g is added, in 90 DEG C of temperature
Hydroxyl hyper-branched polyester UV resin is made in lower insulation reaction 4 hours.
Step c: the end group silicone active body containing double bond and si-h bond simultaneously is catalyzed using the second catalyst
And hydroxyl hyper-branched polyester UV resin reaction, obtain bipolarity dissaving polymer UV matt resin:
Weigh end group in above-mentioned steps (1) the silicone active body 10g containing double bond and si-h bond simultaneously, above-mentioned steps
(2) reaction kettle is added in hydroxyl hyper-branched polyester UV resin 90g and phosphine coordination rhodium complex 0.08g in, and stirring is warming up to 40
DEG C, it reacts 5 hours, bipolarity dissaving polymer UV matt resin is made.
Carrying out ultraviolet light curable to the bipolarity dissaving polymer UV matt resin of above-mentioned preparation can test, and take 20g
Resin is added 0.3g crack type photoinitiator 1- hydroxycyclohexyl phenyl ketone, is uniformly coated on the PET film table that sided corona treatment is crossed
Face, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light and apply
Layer, matt degree are 15.
A kind of bipolarity dissaving polymer UV matt resin, including following component: following mass parts Material synthesis is utilized:
0.1-20 parts of silicone active body simultaneously containing double bond and si-h bond of end group；
80-99.9 parts of UV resin of hydroxyl hyper-branched polyester；
Any 0.05-0.1 parts in chloroplatinic acid or phosphine coordination rhodium complex.
The end group silicone active body containing double bond and si-h bond simultaneously is prepared using the raw material of following mass parts:
2.8-3 parts of vinyl trichlorosilane,
43.7-45 parts of chlorodimethyl silane,
150-300 parts of ether,
10-15 parts of water；
Hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid,
Catalyst triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-diethyl piperazine
Piperazine, N-ethylmorpholine pyridine and one or more of N or N '-dimethyl pyridine；
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or metering system
Any one of acid glycidyl ether；
The catalyst is the 0.1%-2% of dihydromethyl propionic acid quality；The glycidyl acrylate, metering system
The quality of any one of acid glycidyl ester, glycidyl ether or methyl propenoic acid glycidyl ether is dihydroxymethyl
The 10-35% of propionic acid quality.
The embodiment that resin structure invention provides is identical as embodiment of the method, repeats no more.
Compared with prior art, foregoing invention has the advantage that
(1) product is 100% solid content, and solvent-free and VOC is environmentally protective.
(2) product is one-component, is not necessarily to the inorganic delustring auxiliary agents such as outer addition silica, can play matt effect.
(3) in resin structure simultaneously the section of apolar chain containing polysiloxane and the polyester polarity segment containing hydroxyl.It is this
Polysiloxanes segment self-constriction during photocuring of the UV resin of structure forms the exposed nanoscale microballoon of siloxanes segment,
It is embedded in the space three-dimensional network structure that hyper-branched polyester is formed, plays matt effect.
Above to a kind of bipolarity dissaving polymer UV matt process for preparing resins provided by the present invention and the resin
It is described in detail, for those of ordinary skill in the art, thought according to an embodiment of the present invention, in specific embodiment
And there will be changes in application range, in conclusion the contents of this specification are not to be construed as limiting the invention.
Claims (10)
1. a kind of bipolarity dissaving polymer UV matt process for preparing resins, which comprises the steps of:
Step a: the end group silicone active body containing double bond and si-h bond simultaneously is prepared using the following raw material:
Vinyl trichlorosilane,
Chlorodimethyl silane,
Ether and water；
Step b: hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid,
First catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or methacrylic acid contracting
Any one of water glycerin ether；
Step c: silicone active body using the catalysis end group of the second catalyst simultaneously containing double bond and si-h bond and
Hydroxyl hyper-branched polyester UV resin reaction obtains bipolarity dissaving polymer UV matt resin.
2. a kind of bipolarity dissaving polymer UV matt process for preparing resins according to claim 1, which is characterized in that
The end group silicone active body containing double bond and si-h bond simultaneously, hydroxyl hyper-branched polyester UV resin and the second catalysis
The mass parts of agent are as follows:
0.1-20 parts of silicone active body simultaneously containing double bond and si-h bond of end group,
80-99.9 parts of UV resin of hydroxyl hyper-branched polyester,
Second 0.05-0.1 parts of catalyst.
3. a kind of bipolarity dissaving polymer UV matt process for preparing resins according to claim 2, which is characterized in that
First catalyst is triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-diethyl
Piperazine, N-ethylmorpholine pyridine and one or more of N or N '-dimethyl pyridine；
Second catalyst is that chloroplatinic acid or phosphine are coordinated one of rhodium complex.
4. a kind of bipolarity dissaving polymer UV matt process for preparing resins according to claim 3, which is characterized in that
The preparation step of silicone active body of the end group simultaneously containing double bond and si-h bond includes:
Vinyl trichlorosilane, chlorodimethyl silane, ether and water are added in reaction kettle after weighing proportionally, under the conditions of T1
Stirring n1 hours；
It is warming up to T2, decompression vacuum pumping water removal and solvent ether, it is living containing the organosilicon of double bond and si-h bond simultaneously that end group is made
Property body.
5. a kind of bipolarity dissaving polymer UV matt process for preparing resins according to claim 3, which is characterized in that
The mass parts of the vinyl trichlorosilane, chlorodimethyl silane, ether and water are as follows:
2.8-3 parts of vinyl trichlorosilane,
43.7-45 parts of chlorodimethyl silane,
150-300 parts of ether,
10-15 parts of water.
6. a kind of bipolarity dissaving polymer UV matt process for preparing resins according to claim 5, which is characterized in that
The preparation step of the hydroxyl hyper-branched polyester UV resin includes:
Dihydromethyl propionic acid is added in reaction kettle, and the first catalyst is added, and stirring is warming up to T3 in n2 hours, reacts n3 hours,
End carboxyl super branched polyester is made；
By glycidyl acrylate, glycidyl methacrylate, glycidyl ether or Glycidyl methacrylate
The reaction kettle that end carboxyl super branched polyester is made is added in any one of glycerin ether, insulation reaction n4 hours at a temperature of T4, system
Obtain hydroxyl hyper-branched polyester UV resin.
7. a kind of bipolarity dissaving polymer UV matt process for preparing resins according to claim 6, which is characterized in that
First catalyst is the 0.1%-2% of dihydromethyl propionic acid quality；The glycidyl acrylate, methacrylic acid contracting
The quality of any one of water glyceride, glycidyl ether or methyl propenoic acid glycidyl ether is dihydromethyl propionic acid
The 10-35% of quality.
8. a kind of bipolarity dissaving polymer UV matt process for preparing resins according to claim 7, which is characterized in that
The T1 is 30 DEG C of any temperature values in -50 DEG C of sections；The n1 is -6 hours 4 hours any durations；The T2 is 100 DEG C -150
DEG C any temperature value in section；The n2 is -1 hour 0 hour any duration；The T3 is 90 DEG C of any temperature in -130 DEG C of sections
Value；The n3 is -8 hours 4 hours any durations；The T4 is 90 DEG C of any temperature values in -130 DEG C of sections；The n be 2 hours-
4 hours any durations.
9. a kind of bipolarity dissaving polymer UV matt resin, which is characterized in that utilize following mass parts Material synthesis:
0.1-20 parts of silicone active body simultaneously containing double bond and si-h bond of end group；
80-99.9 parts of UV resin of hydroxyl hyper-branched polyester；
Any 0.05-0.1 parts in chloroplatinic acid or phosphine coordination rhodium complex.
10. a kind of bipolarity dissaving polymer UV matt resin, which is characterized in that prepare end using the raw material of following mass parts
The base silicone active body containing double bond and si-h bond simultaneously:
2.8-3 parts of vinyl trichlorosilane,
43.7-45 parts of chlorodimethyl silane,
150-300 parts of ether,
10-15 parts of water；
Hydroxyl hyper-branched polyester UV resin is prepared using the following raw material:
Dihydromethyl propionic acid,
And catalyst triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-diethyl piperazine
Piperazine, N-ethylmorpholine pyridine and one or more of N or N '-dimethyl pyridine；
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or methacrylic acid contracting
Any one of water glycerin ether；
The catalyst is the 0.1%-2% of dihydromethyl propionic acid quality；The glycidyl acrylate, methacrylic acid contracting
The quality of any one of water glyceride, glycidyl ether or methyl propenoic acid glycidyl ether is dihydromethyl propionic acid
The 10-35% of quality.
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