CN110183669A - A kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method and the resin - Google Patents
A kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method and the resin Download PDFInfo
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- CN110183669A CN110183669A CN201910482379.7A CN201910482379A CN110183669A CN 110183669 A CN110183669 A CN 110183669A CN 201910482379 A CN201910482379 A CN 201910482379A CN 110183669 A CN110183669 A CN 110183669A
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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
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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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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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
Abstract
The invention discloses a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method and the resins, prepare end-vinyl ultra-branching polysiloxanes using vinyl trichlorosilane, chlorodimethyl silane, acrylic acid, (methyl) glycidyl acrylate (ether)；Utilizing trimellitic anhydride, diethylene glycol (DEG), methyl) glycidyl acrylate (ether) prepares end-vinyl ultra-branching polyester.Resin polysiloxanes segment self-constriction during photocuring 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.Siloxane molecule segment and polyester molecule segment are Bu Tong overturn to material surface naturally due to polar, are formed antifouling segment in film surface, are played anti-fouling effect.
Description
Technical field
The present invention relates to UV solidified resins to synthesize field technical field, more particularly, to a kind of amphiphilic hyper-branched knot
Structure UV matt antifouling resin preparation method and the resin.
Background technique
Since its is environmentally protective, VOC free discharge, low power consuming solidifies the advantages that quick, becomes future UV photocuring technology
Green coating material new technology with development potential.With the upgrading of social industrial level and people's level of consumption, consumer
The appearance of articles for daily use and industrial goods, sense of touch, experience comfort level are required increasingly harsher.It is many top grade articles, start with
Beautiful, comfortable shape and sense of touch attract public attention.The application of matt coating is also just come into being.It is with the outer of beauty
Table, comfortable Human physiology sense of touch gradually gain a place in industries such as automobile interior decoration, electronic products, and increasingly obtain
More favors.Furthermore fields such as monitoring, outdoor display screen curtain, curtain wall outdoors, it is desirable that material has good antifouling dust-proof
Effect.
Preparing the universal method of anti-fouling type coating at present is to add a certain amount of organosilicon polymer in the coating, such outer
Although the method for addition auxiliary agent can be improved the anti-fouling effect of coating, but organosilicon external additive and UV resin system is compatible
Property is bad, and with the extension of use time, organosilicon can be precipitated, and influence the service performance of product.UV solidifies matt coating at present
The preparation of material relies primarily on addition inorganic filler, i.e., a certain amount of delustring auxiliary agent is added into the system of coating, predominantly respectively
Silica or aluminum oxide of kind partial size etc., these fillers can reach matt effect by photoextinction.But it is added
Inorganic filler and the organic system of coating be difficult perfection and dissolve each other, such as necessarily there are separating at the unstable states in long-term place, rear
With in use, being located at container bottom since the sedimentation of filler may cause inorganic filler, the coating for influencing the later period is imitated for the storage of phase
Fruit 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, do not add organic silicon and help
Agent, resin itself carry the UV solidified resin of matt effect and anti-fouling effect.
Summary of the invention
In view of the above problems, the invention proposes a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method and
The resin, using in this resin contain end-vinyl ultra-branching polysiloxanes and end-vinyl ultra-branching polyester.In photocuring
The self-constriction of polysiloxanes segment forms the exposed nanoscale microballoon of siloxanes segment, the sky that insertion hyper-branched polyester is formed in the process
Between in three-dimensional net structure, play matt effect.Siloxane molecule segment and polyester molecule segment are due to polar Bu Tong natural
Overturning forms antifouling segment in film surface, plays anti-fouling effect to material surface.
The present invention provides a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method, includes the following steps:
Step a: end-vinyl ultra-branching polysiloxanes is prepared using the following raw material:
Vinyl trichlorosilane,
Chlorodimethyl silane,
Ether,
Water,
First catalyst,
Acrylic acid,
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether and metering system
Any one of acid glycidyl ether；
Step b: end-vinyl ultra-branching polyester is prepared using the following raw material:
Trimellitic anhydride,
Diethylene glycol (DEG),
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether and metering system
Any one of acid glycidyl ether；
Step c: resulting end-vinyl ultra-branching polysiloxanes and end-vinyl ultra-branching polyester are mixed.
The mass parts of the end-vinyl ultra-branching polysiloxanes and end-vinyl ultra-branching polyester are as follows:
Further, end-vinyl ultra-branching polysiloxanes 10-60 parts, 40-90 parts of end-vinyl ultra-branching polyester.
Further, first catalyst is hydrosilylation catalyst.
Further, second catalyst includes triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl
Cyclohexylamine, N, N '-diethyl piperazine, N-ethylmorpholine pyridine or N, one or more of N '-dimethyl pyridine.
Further, the end-vinyl ultra-branching polysiloxanes step for preparing includes:
Vinyl trichlorosilane, chlorodimethyl silane, ether, water, the first catalyst are weighed according to the mass parts of setting
It is stirred n1 hours under the conditions of temperature T1；
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；
Acrylic acid, nitrogen protection is added, temperature is adjusted to T3, reacted n2 hours；
The second catalyst is added, addition glycidyl acrylate, glycidyl methacrylate, acrylic acid shrink sweet
Any one of oily ether and methyl propenoic acid glycidyl ether insulation reaction n3 hours, measure system acid value, and acid value reaches 2-
3mgKOH/g stops reaction.
Further, the vinyl trichlorosilane, chlorodimethyl silane, ether, water, the first catalyst, acrylic acid,
The mass parts of glycidyl acrylate and the second catalyst 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,
First 0.1-1 parts of catalyst,
Acrylic acid: 50-55 parts,
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether and methacrylic acid contracting
Any 20-40 parts in water glycerin ether,
Second 0.01-1 parts of catalyst.
Further, the vinyl ultra-branching polyester step for preparing includes:
Trimellitic anhydride and diethylene glycol (DEG) are added the second catalyst, stirred according to equimolar than being added in reaction kettle after weighing
It mixes, T4 is warming up in n4 hours, react n5 hours, end carboxyl super branched polyester is made；
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether and metering system is added
Any one of acid glycidyl ether insulation reaction n6 hours, measures system acid value, and acid value, which reaches 2-3mgKOH/g, to be stopped instead
It answers.
Second catalyst loading is the 0.1%-2% of trimellitic anhydride and diethylene glycol (DEG) gross mass, the acrylic acid
Appointing in ethylene oxidic ester, glycidyl methacrylate, glycidyl ether and methyl propenoic acid glycidyl ether
A kind of additive amount is the 10-35% of trimellitic anhydride and diethylene glycol (DEG) gross mass.
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 T3 is 90 DEG C of any temperature values in -98 DEG C of sections；The n2 is 4 small
When -6 hours any durations；The n3 is -6 hours 4 hours any durations；For in 1 hour in described n4 hours；The T4 is 90
DEG C any temperature value in -130 DEG C of sections, the n5 are -8 hours 4 hours any durations；When the n6 is -6 hours 4 hours any
It is long.
A kind of amphiphilic hyper-branched structure UV matt antifouling resin, including following component:
10-60 parts of end-vinyl ultra-branching polysiloxanes,
40-90 parts of end-vinyl ultra-branching polyester；
The end-vinyl ultra-branching polysiloxanes is synthesized using following component:
2.8-3 parts of vinyl trichlorosilane；
43.7-45 parts of chlorodimethyl silane,
150-300 parts of ether,
10-15 parts of water,
First catalyst: 0.1-1 parts of hydrosilylation catalyst,
50-55 parts of acrylic acid,
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether or methacrylic acid contracting
Any 20-40 parts in water glycerin ether,
Second catalyst: triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-diethyl
Base piperazine, N-ethylmorpholine pyridine and one of N or N '-dimethyl pyridine or 0.01-1 parts a variety of；
The end-vinyl ultra-branching polysiloxanes is synthesized using following component:
The trimellitic anhydride and diethylene glycol (DEG) of equimolar ratio,
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or metering system
Any one of acid glycidyl ether；
The additive amount of second catalyst is the 0.1%-2% of trimellitic anhydride and diethylene glycol (DEG) gross mass, the propylene
Acid glycidyl ester, in glycidyl methacrylate, glycidyl ether or methyl propenoic acid glycidyl ether
Any additive amount is the 10-35% of trimellitic anhydride and diethylene glycol (DEG) gross mass.
A kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method of the invention and the resin utilize end-vinyl
Polysiloxanes segment self-constriction during photocuring of hyperbranched polyorganosiloxane and end-vinyl ultra-branching polyester forms silicon oxygen
The exposed nanoscale microballoon of alkane segment is embedded in the space three-dimensional network structure that hyper-branched polyester is formed, plays matt effect.Silicon
Oxygen alkane molecule segment and polyester molecule segment are Bu Tong overturn to material surface naturally due to polar, form antifouling chain in film surface
Section, plays anti-fouling effect.
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 amphiphilic hyper-branched structure UV matt antifouling resin preparation method, includes the following steps:
Step a: end-vinyl ultra-branching polysiloxanes is prepared using the following raw material:
Vinyl trichlorosilane,
Chlorodimethyl silane,
Ether,
Water,
First catalyst,
Acrylic acid,
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether and metering system
Any one of acid glycidyl ether；
Step b: end-vinyl ultra-branching polyester is prepared using the following raw material:
Trimellitic anhydride,
Diethylene glycol (DEG),
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether and metering system
Any one of acid glycidyl ether；
Step c: resulting end-vinyl ultra-branching polysiloxanes and end-vinyl ultra-branching polyester are mixed.
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..
Using in this resin contain end-vinyl ultra-branching polysiloxanes and end-vinyl ultra-branching polyester.In photocuring
The self-constriction of polysiloxanes segment forms the exposed nanoscale microballoon of siloxanes segment, the sky that insertion hyper-branched polyester is formed in the process
Between in three-dimensional net structure, play matt effect.Siloxane molecule segment and polyester molecule segment are due to polar Bu Tong natural
Overturning forms antifouling segment in film surface, plays anti-fouling effect to material surface.
The mass parts of the end-vinyl ultra-branching polysiloxanes and end-vinyl ultra-branching polyester are as follows:
10-60 parts of end-vinyl ultra-branching polysiloxanes,
40-90 parts of end-vinyl ultra-branching polyester.
First catalyst is hydrosilylation catalyst, can be chloroplatinic acid, phosphine coordination rhodium complex etc.；Described second
Catalyst includes triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-diethyl piperazine, N-
Ethyl morpholine pyridine or N, one or more of N '-dimethyl pyridine.
The end-vinyl ultra-branching polysiloxanes step for preparing includes:
Vinyl trichlorosilane, chlorodimethyl silane, ether, water, the first catalyst are weighed according to the mass parts of setting
It is stirred n1 hours under the conditions of temperature T1；
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；
Acrylic acid, nitrogen protection is added, temperature is adjusted to T3, reacted n2 hours；
The second catalyst is added, addition glycidyl acrylate, glycidyl methacrylate, acrylic acid shrink sweet
Any one of oily ether and methyl propenoic acid glycidyl ether insulation reaction n3 hours, measure system acid value, and acid value reaches 2-
3mgKOH/g stops reaction.
The vinyl trichlorosilane, chlorodimethyl silane, ether, water, the first catalyst, acrylic acid, acrylic acid contracting
The mass parts of water glyceride and the second catalyst 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,
First 0.1-1 parts of catalyst,
Acrylic acid: 50-55 parts,
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether and methacrylic acid contracting
Any 20-40 parts in water glycerin ether,
Second 0.01-1 parts of catalyst.
The vinyl ultra-branching polyester step for preparing includes:
Trimellitic anhydride and diethylene glycol (DEG) are added the second catalyst, stirred according to equimolar than being added in reaction kettle after weighing
It mixes, T4 is warming up in n4 hours, react n5 hours, end carboxyl super branched polyester is made；
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether and metering system is added
Any one of acid glycidyl ether insulation reaction n6 hours, measures system acid value, and acid value, which reaches 2-3mgKOH/g, to be stopped instead
It answers.
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 T3 is 90 DEG C of any temperature values in -98 DEG C of sections；The n2 is -6 hours 4 hours
Any duration；The n3 is -6 hours 4 hours any durations；For in 1 hour in described n4 hours；The T4 is 90 DEG C -130 DEG C
Any temperature value in section, the n5 are -8 hours 4 hours any durations；The n6 is -6 hours 4 hours any durations.
Embodiment one:
Step a: end-vinyl ultra-branching polysiloxanes is prepared:
Weigh vinyl trichlorosilane 2.8g, chlorodimethyl silane 45g, ether 150g, catalyst chloroplatinic acid 0.1g and
Water 10g is added in reaction kettle, stirs 6 hours under the conditions of 30 DEG C；100 DEG C are warming up to, decompression vacuum pumping removes water and solvent ether.Add
Enter acrylic acid 50g, nitrogen protection, temperature is adjusted to 90 DEG C, is reacted 6 hours.Catalyst triphenylphosphine 0.01g is added, is added third
Olefin(e) acid ethylene oxidic ester 20g insulation reaction 4 hours, measures system acid value, and acid value reaches 2mgKOH/g and stops reaction.Prepare end
Vinyl ultra-branching polysiloxanes.
Step b: end-vinyl ultra-branching polyester is prepared:
It weighs trimellitic anhydride 181.7g, diethylene glycol (DEG) 100.3g and triphenylphosphine 0.282g is added in reaction kettle, 30 minutes
90 DEG C are warming up to, reacts 8 hours, end carboxyl super branched polyester is made；Glycidyl acrylate 28.2g, insulation reaction 6 is added
Hour, system acid value is measured, acid value reaches 2mgKOH/g and stops reaction.End-vinyl ultra-branching polyester is made.
Step c: amphiphilic hyper-branched structure UV matt antifouling resin is prepared:
The end-vinyl ultra-branching polyester of end-vinyl ultra-branching polysiloxanes and step b preparation prepared by step a is pressed
It is mixed according to mass ratio 1:9.
Carrying out ultraviolet light curable to the amphiphilic hyper-branched structure UV matt antifouling 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 that sided corona treatment is crossed
Film surface, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light
Coating.Its matt degree is 23, and water contact angle is 99 °.
Embodiment two:
Step a: end-vinyl ultra-branching polysiloxanes is prepared:
Weigh vinyl trichlorosilane 3g, chlorodimethyl silane 43.7g, ether 300g, catalyst chloroplatinic acid 1g and water
15g is added in reaction kettle, stirs 4 hours under the conditions of 50 DEG C；150 DEG C are warming up to, decompression vacuum pumping removes water and solvent ether.It is added
Acrylic acid 55g, nitrogen protection, temperature are adjusted to 98 DEG C, are reacted 4 hours.Catalyst of triethylamine 1g is added, methacrylic acid is added
Ethylene oxidic ester 40g insulation reaction 6 hours, measures system acid value, and acid value reaches 3mgKOH/g and stops reaction.Prepare end ethylene
Base hyperbranched polyorganosiloxane.
Step b: end-vinyl ultra-branching polyester is prepared:
It weighs trimellitic anhydride 181.7g, diethylene glycol (DEG) 100.3g and triethanolamine 5.64g is added in reaction kettle, rise within 60 minutes
Temperature reacts 4 hours to 130 DEG C, end carboxyl super branched polyester is made；Glycidyl methacrylate 98.7g is added, heat preservation is anti-
It answers 4 hours, measures system acid value, acid value reaches 3mgKOH/g and stops reaction.End-vinyl ultra-branching polyester is made.
Step c: amphiphilic hyper-branched structure UV matt antifouling resin is prepared:
The end-vinyl ultra-branching polyester of end-vinyl ultra-branching polysiloxanes and step b preparation prepared by step a is pressed
It is mixed according to mass ratio 2:8.
Carrying out ultraviolet light curable to the amphiphilic hyper-branched structure UV matt antifouling 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 that sided corona treatment is crossed
Film surface, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light
Coating.Its matt degree is 21, and water contact angle is 100 °.
Embodiment three:
Step a: end-vinyl ultra-branching polysiloxanes is prepared:
Weigh vinyl trichlorosilane 3g, chlorodimethyl silane 44g, ether 200g, catalyst phosphine coordination rhodium complex
0.3g and water 12g is added in reaction kettle, stirs 5 hours under the conditions of 40 DEG C；130 DEG C are warming up to, decompression vacuum pumping removes water and solvent
Ether.Acrylic acid 53g, nitrogen protection is added, temperature is adjusted to 95 DEG C, is reacted 5 hours.Catalyst triethanolamine 0.2g is added,
Methyl propenoic acid glycidyl ether 39g is added, insulation reaction 5 hours, measures system acid value, acid value reaches 2.4mgKOH/g stopping
Reaction.Prepare end-vinyl ultra-branching polysiloxanes.
Step b: end-vinyl ultra-branching polyester is prepared:
Trimellitic anhydride 181.7g, diethylene glycol (DEG) 100.3g and N are weighed, N '-diethyl piperazine 5g is added in reaction kettle, and 40 points
Clock is warming up to 120 DEG C, reacts 5 hours, end carboxyl super branched polyester is made；Methyl propenoic acid glycidyl ether 56g, heat preservation is added
Reaction 5 hours, measures system acid value, and acid value reaches 2.3mgKOH/g and stops reaction.End-vinyl ultra-branching polyester is made.
Step c: amphiphilic hyper-branched structure UV matt antifouling resin is prepared:
The end-vinyl ultra-branching polyester of end-vinyl ultra-branching polysiloxanes and step b preparation prepared by step a is pressed
It is mixed according to mass ratio 3:7.
Carrying out ultraviolet light curable to the amphiphilic hyper-branched structure UV matt antifouling 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 that sided corona treatment is crossed
Film surface, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light
Coating.Its matt degree is 20, and water contact angle is 101 °.
Example IV:
Step a: end-vinyl ultra-branching polysiloxanes is prepared:
Weigh vinyl trichlorosilane 3g, chlorodimethyl silane 44g, ether 180g, catalyst phosphine coordination rhodium complex
0.4g and water 11g is added in reaction kettle, stirs 5 hours under the conditions of 40 DEG C；130 DEG C are warming up to, decompression vacuum pumping removes water and solvent
Ether.Acrylic acid 52g, nitrogen protection is added, temperature is adjusted to 95 DEG C, is reacted 5 hours.Add catalyst n, N '-dimethyl pyrrole
Pyridine 0.2g is added glycidyl ether 39g, insulation reaction 5 hours, measures system acid value, acid value reaches 2.5mgKOH/g
Stop reaction.Prepare end-vinyl ultra-branching polysiloxanes.
Step b: end-vinyl ultra-branching polyester is prepared:
Trimellitic anhydride 181.7, diethylene glycol (DEG) 100.3g and N are weighed, N '-diethyl piperazine 5g is added in reaction kettle, and 40 points
Clock is warming up to 120 DEG C, reacts 5 hours, end carboxyl super branched polyester is made；Glycidyl ether 54g, insulation reaction is added
5 hours, system acid value is measured, acid value reaches 2.5mgKOH/g and stops reaction.End-vinyl ultra-branching polyester is made.
Step c: amphiphilic hyper-branched structure UV matt antifouling resin is prepared:
The end-vinyl ultra-branching polyester of end-vinyl ultra-branching polysiloxanes and step b preparation prepared by step a is pressed
It is mixed according to mass ratio 4:6.
Carrying out ultraviolet light curable to the amphiphilic hyper-branched structure UV matt antifouling 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 that sided corona treatment is crossed
Film surface, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light
Coating.Its matt degree is 19, and water contact angle is 101.5 °.
Embodiment five:
Step a: end-vinyl ultra-branching polysiloxanes is prepared:
Weigh vinyl trichlorosilane 3g, chlorodimethyl silane 44g, ether 160g, catalyst phosphine coordination rhodium complex
0.3g and water 10g is added in reaction kettle, stirs 5 hours under the conditions of 40 DEG C；130 DEG C are warming up to, decompression vacuum pumping removes water and solvent
Ether.Acrylic acid 54g, nitrogen protection is added, temperature is adjusted to 95 DEG C, is reacted 5 hours.Add catalyst n-ethyl morpholine pyridine
0.2g is added glycidyl acrylate ether 40g, insulation reaction 5 hours, measures system acid value, acid value reaches 2.6mgKOH/g
Stop reaction.Prepare end-vinyl ultra-branching polysiloxanes.
Step b: end-vinyl ultra-branching polyester is prepared:
It weighs trimellitic anhydride 181.7g, diethylene glycol (DEG) 100.3g and N-ethylmorpholine pyridine 5g is added in reaction kettle, 40 points
Clock is warming up to 120 DEG C, reacts 5 hours, end carboxyl super branched polyester is made；Glycidyl acrylate 54g, insulation reaction is added
5 hours, system acid value is measured, acid value reaches 2.6mgKOH/g and stops reaction.End-vinyl ultra-branching polyester is made.
Step c: amphiphilic hyper-branched structure UV matt antifouling resin is prepared:
The end-vinyl ultra-branching polyester of end-vinyl ultra-branching polysiloxanes and step b preparation prepared by step a is pressed
It is mixed according to mass ratio 5:5.
Carrying out ultraviolet light curable to the amphiphilic hyper-branched structure UV matt antifouling 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 that sided corona treatment is crossed
Film surface, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light
Coating.Its matt degree is 17, and water contact angle is 102 °.
Embodiment six:
Step a: end-vinyl ultra-branching polysiloxanes is prepared:
Weigh vinyl trichlorosilane 3g, chlorodimethyl silane 44g, ether 170g, catalyst chloroplatinic acid 0.3g and water
13g is added in reaction kettle, stirs 5 hours under the conditions of 40 DEG C；130 DEG C are warming up to, decompression vacuum pumping removes water and solvent ether.It is added
Acrylic acid 52.6g, nitrogen protection, temperature are adjusted to 95 DEG C, are reacted 5 hours.Add catalyst n, N- dimethyl cyclohexyl amine 0.2g,
Glycidyl ether 40g is added, insulation reaction 5 hours, measures system acid value, acid value, which reaches 2.7mgKOH/g, to be stopped instead
It answers.Prepare end-vinyl ultra-branching polysiloxanes.
Step b: end-vinyl ultra-branching polyester is prepared:
Trimellitic anhydride 181.7g, diethylene glycol (DEG) 100.3g and N are weighed, N- dimethyl cyclohexyl amine 5g is added in reaction kettle, and 40
Minute is warming up to 120 DEG C, reacts 5 hours, end carboxyl super branched polyester is made；Glycidyl ether 54g is added, heat preservation is anti-
It answers 5 hours, measures system acid value, acid value reaches 2.7mgKOH/g and stops reaction.End-vinyl ultra-branching polyester is made.
Step c: amphiphilic hyper-branched structure UV matt antifouling resin is prepared:
The end-vinyl ultra-branching polyester of end-vinyl ultra-branching polysiloxanes and step b preparation prepared by step a is pressed
It is mixed according to mass ratio 6:4.
Carrying out ultraviolet light curable to the amphiphilic hyper-branched structure UV matt antifouling 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 that sided corona treatment is crossed
Film surface, the uv cure machine solidification 10s that 25 μm of coating layer thickness are 1000W with power solidify flexible matt to get ultraviolet light
Coating.Its matt degree is 13, and water contact angle is 104 °.
A kind of amphiphilic hyper-branched structure UV matt antifouling resin, including following component:
10-60 parts of end-vinyl ultra-branching polysiloxanes,
40-90 parts of end-vinyl ultra-branching polyester；
The end-vinyl ultra-branching polysiloxanes is synthesized using following component:
2.8-3 parts of vinyl trichlorosilane；
43.7-45 parts of chlorodimethyl silane,
150-300 parts of ether,
10-15 parts of water,
First catalyst: 0.1-1 parts of hydrosilylation catalyst, the hydrosilylation catalyst includes but does not limit to chlorine platinum
Acid, phosphine are coordinated rhodium complex,
50-55 parts of acrylic acid,
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether or methacrylic acid contracting
Any 20-40 parts in water glycerin ether,
Second catalyst: triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-diethyl
Base piperazine, N-ethylmorpholine pyridine and one of N or N '-dimethyl pyridine or 0.01-1 parts a variety of；
The end-vinyl ultra-branching polysiloxanes is synthesized using following component:
The trimellitic anhydride and diethylene glycol (DEG) of equimolar ratio,
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or metering system
Any one of acid glycidyl ether；
The additive amount of second catalyst is the 0.1%-2% of trimellitic anhydride and diethylene glycol (DEG) gross mass, the propylene
Acid glycidyl ester, in glycidyl methacrylate, glycidyl ether or methyl propenoic acid glycidyl ether
Any additive amount is the 10-35% of trimellitic anhydride and diethylene glycol (DEG) gross mass.
The embodiment that resin structure invention provides is identical as embodiment of the method, repeats no more.Compared with prior art, above-mentioned
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.
(4) the siloxane molecule segment for playing anti-fouling effect enters resin system, silicon oxygen not by the mode of outer addition
Due to polar difference, the coating itself of overturning to material surface naturally, preparation has anti-fouling effect for alkane segment and polyester segment.
Above to a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method provided by the present invention and the tree
Rouge is described in detail, for those of ordinary skill in the art, thought according to an embodiment of the present invention, in specific embodiment party
There will be changes in formula and application range, in conclusion the contents of this specification are not to be construed as limiting the invention.
Claims (10)
1. a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method, which comprises the steps of:
Step a: end-vinyl ultra-branching polysiloxanes is prepared using the following raw material:
Vinyl trichlorosilane,
Chlorodimethyl silane,
Ether,
Water,
First catalyst,
Acrylic acid,
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether and methacrylic acid contracting
Any one of water glycerin ether；
Step b: end-vinyl ultra-branching polyester is prepared using the following raw material:
Trimellitic anhydride,
Diethylene glycol (DEG),
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether and methacrylic acid contracting
Any one of water glycerin ether；
Step c: resulting end-vinyl ultra-branching polysiloxanes and end-vinyl ultra-branching polyester are mixed.
2. amphiphilic hyper-branched structure UV matt antifouling resin preparation method according to claim 1, which is characterized in that institute
State the mass parts of end-vinyl ultra-branching polysiloxanes Yu end-vinyl ultra-branching polyester are as follows:
10-60 parts of end-vinyl ultra-branching polysiloxanes,
40-90 parts of end-vinyl ultra-branching polyester.
3. a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method according to claim 2, feature exist
In first catalyst is hydrosilylation catalyst.
4. a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method according to claim 3, feature exist
In second catalyst includes triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-two
Ethyl piperazidine, N-ethylmorpholine pyridine or N, one or more of N '-dimethyl pyridine.
5. a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method according to claim 1-4,
It is characterized in that, the end-vinyl ultra-branching polysiloxanes step for preparing includes:
Vinyl trichlorosilane is weighed according to the mass parts of setting, chlorodimethyl silane, ether, water, the first catalyst is in temperature
It is stirred n1 hours under the conditions of degree T1；
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；
Acrylic acid, nitrogen protection is added, temperature is adjusted to T3, reacted n2 hours；
The second catalyst is added, glycidyl acrylate, glycidyl methacrylate, glycidyl ether is added
Any one of with methyl propenoic acid glycidyl ether, insulation reaction n3 hours, system acid value is measured, acid value reaches 2-
3mgKOH/g stops reaction.
6. a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method according to claim 5, feature exist
In, the vinyl trichlorosilane, chlorodimethyl silane, ether, water, the first catalyst, acrylic acid, glycidyl
The mass parts of ester and the second catalyst 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,
First 0.1-1 parts of catalyst,
Acrylic acid: 50-55 parts,
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether and Glycidyl methacrylate are sweet
Any 20-40 parts in oily ether,
Second 0.01-1 parts of catalyst.
7. a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method according to claim 6, feature exist
In the vinyl ultra-branching polyester step for preparing includes:
The second catalyst, stirring, n4 is added than being added in reaction kettle after weighing according to equimolar in trimellitic anhydride and diethylene glycol (DEG)
It is warming up to T4 in hour, reacts n5 hours, end carboxyl super branched polyester is made；
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether and methacrylic acid contracting is added
Any one of water glycerin ether insulation reaction n6 hours, measures system acid value, and acid value reaches 2-3mgKOH/g and stops reaction.
8. special according to a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method described in claim requirement 7
Sign is that second catalyst loading is the 0.1%-2% of trimellitic anhydride and diethylene glycol (DEG) gross mass, the acrylic acid contracting
Any in water glyceride, glycidyl methacrylate, glycidyl ether and methyl propenoic acid glycidyl ether
Kind additive amount is the 10-35% of trimellitic anhydride and diethylene glycol (DEG) gross mass.
9. a kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method according to claim 8, feature exist
In 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 be 100 DEG C-
150 DEG C of any temperature values in section；The T3 is 90 DEG C of any temperature values in -98 DEG C of sections；When the n2 is -6 hours 4 hours any
It is long；The n3 is -6 hours 4 hours any durations；For in 1 hour in described n4 hours；The T4 is that 90 DEG C of -130 DEG C of sections are appointed
One temperature value, the n5 are -8 hours 4 hours any durations；The n6 is -6 hours 4 hours any durations.
10. a kind of amphiphilic hyper-branched structure UV matt antifouling resin, which is characterized in that including following component:
10-60 parts of end-vinyl ultra-branching polysiloxanes,
40-90 parts of end-vinyl ultra-branching polyester；
The end-vinyl ultra-branching polysiloxanes is synthesized using following component:
2.8-3 parts of vinyl trichlorosilane；
43.7-45 parts of chlorodimethyl silane,
150-300 parts of ether,
10-15 parts of water,
First catalyst: 0.1-1 parts of hydrosilylation catalyst,
50-55 parts of acrylic acid,
Glycidyl acrylate, glycidyl methacrylate, glycidyl ether or Glycidyl methacrylate are sweet
Any 20-40 parts in oily ether,
Second catalyst: triphenylphosphine, triethylamine, triethanolamine, ammonium chloride, N, N- dimethyl cyclohexyl amine, N, N '-diethyl piperazine
Piperazine, N-ethylmorpholine pyridine and one of N or N '-dimethyl pyridine or 0.01-1 parts a variety of；
The end-vinyl ultra-branching polysiloxanes is synthesized using following component:
The trimellitic anhydride and diethylene glycol (DEG) of equimolar ratio,
Second catalyst,
And glycidyl acrylate, glycidyl methacrylate, glycidyl ether or methacrylic acid contracting
Any one of water glycerin ether；
The additive amount of second catalyst is the 0.1%-2% of trimellitic anhydride and diethylene glycol (DEG) gross mass, the acrylic acid contracting
Water glyceride, any in glycidyl methacrylate, glycidyl ether or methyl propenoic acid glycidyl ether
Kind additive amount is the 10-35% of trimellitic anhydride and diethylene glycol (DEG) gross mass.
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