CN106995681B - A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof - Google Patents
A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof Download PDFInfo
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- CN106995681B CN106995681B CN201710218160.7A CN201710218160A CN106995681B CN 106995681 B CN106995681 B CN 106995681B CN 201710218160 A CN201710218160 A CN 201710218160A CN 106995681 B CN106995681 B CN 106995681B
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
Abstract
The present invention provides a kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof, the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer includes rosin polymer microballoon and modified gelatin acrylic composite, rosin polymer microballoon includes rosin, gelatin and acrylate copolymer, and modified gelatin acrylic composite is crosslinked to obtain by gelatin and methyl acrylate, N hydroxymethyl acrylamide.Preparation method of the present invention is simple, the material that the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer prepared is selected is mostly that gelatin, rosin etc. are cheap, abundance, environment amenable material, contain two kinds of forms of microballoon and lotion in adhesive, good to the bond properties of timber, spreadability is good, viscosity is protected from environmental small, and comprehensive performance significantly improves.
Description
Technical field
The invention belongs to gelatin adhesive field of material technology, and in particular to a kind of modification of the microballoon containing rosin polymer is bright
Glue acrylic resin adhesive and preparation method thereof.
Background technology
Gelatin is obtained by the collagen partial hydrolysis in Animal Skin, bone, tendon and ligament tissue, is protein fragments
Mixture, be made of 18 kinds of amino acid, the Amphiphatic high polymer polyelectrolyte with protein structure, there is excellent biology drop
Performance, low antigenicity and good biocompatibility are solved, gelatin solution itself also has unique performance, at low temperature can shape
At the hydrogel of physical crosslinking, in photosensitive material, medicine, food, weaving, coating, building materials, dyestuff, electronics industry, cosmetics etc.
There is relatively broad application in field.
Gelatin has had history more remote as adhesive, and gelatin has glue-line setting time short, attached to timber etc.
Put forth effort, glue-joint strength is big, and impregnation is simple, need not add other auxiliary agents, but individually gelatin adhesive viscosity is big, it is not easy to
Brush coating and levelling, and it is easy moisture absorption mildew, viscosity is larger with environmental change.When temperature is increased to the solidification point of gelatin or more
When, gelatin molecule is with arbitrary curly presence, and in solidification point triple-helix structure formed below, gelatin also contains a large amount of dried meat ammonia
Acid, hydroxy-proline and glycine, gelatin chemical reaction can occur with a variety of crosslinking agents and electrostatic interaction forms modified gelatin.
Bioadhesive and preparation method thereof disclosed in Chinese patent CN 104623725B, by transparent phytic acid, chondroitin sulfate
The methacrylate of at least one of element, gelatin, polypeptide, alginic acid and chitosan and oxidation is acrylic ester grafted
It arrives.The bioadhesive has good bioactivity, preferable mechanical property, biodegradable and promotion moist environment group
The advantages that knitting healing.The disclosed composite materials being made of acrylic copolymer and gelatin of Chinese patent CN 101555305A and
Preparation method mixes glycidyl methacrylate, acrylic acid with the copolymer of esters of acrylic acid with aqueous gelatin solution,
Heating stirring, is uniformly mixed and forms composite material.By the above-mentioned prior art it is found that by the Macroscopic single crystals such as gelatin and acrylic acid
Composite adhesive has many advantages, such as environmentally friendly, nontoxic, degradable, but the stability of adhesive medium viscosity, levelability and dry
Dry speed is all difficult to control best.Rosin has larger molecular weight, has 3 six-membered cyclic structures, is conducive to promote compound
Adhesive have the function of new structure and.
Invention content
The technical problem to be solved in the present invention is to provide a kind of modified gelatin acrylic resins of microballoon containing rosin polymer
Rosin polymer microballoon is added in gelatin and acrylic monomers, by rosin polymer microballoon by adhesive and preparation method thereof
It incorporates wherein, improves the performance of modified gelatin acrylic resin adhesive, improve the bonding force to timber, levelling ability reduces
Influence of the viscosity to environment.
In order to solve the above technical problems, the technical scheme is that：
A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer, the microballoon containing rosin polymer
Modified gelatin acrylic resin adhesive includes rosin polymer microballoon and modified gelatin acrylic composite, and the rosin is high
Molecule microballoon includes rosin, gelatin and acrylate copolymer, and the modified gelatin acrylic composite is by gelatin and propylene
Sour methyl esters, N hydroxymethyl acrylamide are crosslinked to obtain, and it is 45% that the modified gelatin acrylic resin adhesive, which is solid content,
Light gray microemulsion thick liquid, viscosity 200-300mPas.
As a preferred embodiment of the above technical solution, the preparation method of the modified gelatin acrylic composite is：By 100 parts
The gelatin solution of 10-15wt% is equipped in the reaction kettle of condensing unit, and 3-5 parts of nitrous acid are added, 40-60min is stirred at 0-5 DEG C,
20min is vacuumized, 25-30 parts of propylene acids monomer mixtures are added, the sodium hydroxide solution that mass fraction is 30% is added, is adjusted
It is warming up to 75-85 DEG C under pH to 6.5-7, stirring rod speed of agitator 100-120r/min, the persulfuric acid of 20-25 parts of 10wt% is added dropwise
Potassium initiator solution, 1-3h are added dropwise, then are warming up to 80-90 DEG C, stop heating after insulation reaction 1-1.5h, and 30wt% is added
Sodium hydroxide solution, adjust pH to 6.5-7, stop heating after insulation reaction 0.5h, be cooled to 40-45 DEG C, obtain modified bright
Glue acrylic composite.
The present invention also provides a kind of preparation method of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer,
Include the following steps：
(1) 5-10 parts of gelatin is added in 500 parts of distilled water, is passed through nitrogen and condensed water, heating water bath to 60-80
DEG C, 30-60min is stirred, cooled to room temperature obtains gelatin solution；
(2) 100 parts of rosin glycidyl methacrylate carboxylate is slowly added to 25-30 parts of propylene acrylic monomers
Mixture and 300 parts of gelatin solutions continue to stir 30-60min, the potassium peroxydisulfate initiator solution and 5- of 2-5 parts of 10wt% are added dropwise
The sodium hydroxide solution of 10 parts of 30wt%, 1-3h are added dropwise, and washing, filtering and drying obtains rosin polymer microballoon；
(3) gelatin solution of 100 parts of 10-15wt% is equipped in the reaction kettle of condensing unit, 3-5 parts of nitrous acid, 0-5 is added
40-60min is stirred at DEG C, vacuumizes 20min, adds 25-30 parts of propylene acids monomer mixtures, and it is 30% that mass fraction, which is added,
Sodium hydroxide solution adjusts pH to 6.5-7, adds rosin polymer microballoon, under stirring rod speed of agitator 100-120r/min
It is warming up to 75-85 DEG C, the potassium peroxydisulfate initiator solution of 20-25 parts of 10wt% is added dropwise, 1-3h is added dropwise, then is warming up to 80-
90 DEG C, stop heating after insulation reaction 1-1.5h, the sodium hydroxide solution of 30wt% is added, adjusts pH to 6.5-7, insulation reaction
Stop heating after 0.5h, is cooled to 40-45 DEG C, obtains the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer.
As a preferred embodiment of the above technical solution, in the step (1), gelatin is that the industry of alkaline process manufacture is bright in gelatin solution
Glue, molecular mass are 4-8 ten thousand.
As a preferred embodiment of the above technical solution, in the step (2) or step (3), the propylene acrylic monomer mixing
Object is made of methyl acrylate and N hydroxymethyl acrylamide, wherein the mass ratio of methyl acrylate and N hydroxymethyl acrylamide
For 15-20:8-10.
As a preferred embodiment of the above technical solution, it in the step (2), washs and is cleaned for warm water.
As a preferred embodiment of the above technical solution, dry for the dry 12h in 40-50 DEG C of baking oven in the step (2).
As a preferred embodiment of the above technical solution, in the step (3), the modified gelatin acrylic acid of the microballoon containing rosin polymer
The mass fraction of rosin polymer microballoon is 5-25% in resin binder.
As a preferred embodiment of the above technical solution, in the step (3), the modified gelatin acrylic acid of the microballoon containing rosin polymer
Modified gelatin acrylic resin adhesive is the light gray microemulsion thick liquid that solid content is 45%, viscosity in resin binder
For 200-300mPas.
As a preferred embodiment of the above technical solution, in the step (3), the modified gelatin acrylic acid of the microballoon containing rosin polymer
Resin binder is bonded for plank.
Compared with prior art, the invention has the advantages that：
(1) primary raw material is in the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer prepared by the present invention
Modified gelatin acrylic resin compound material, for gelatin after nitrite-oxidizing processing, part hydrophile amino is transformed into hydroxyl, reduces
The viscous force of gelatin solution, improves the water resistance of gelatin, then polymerize with N hydroxymethyl acrylamide with methyl acrylate, by hydroxyl
Methyl and collagen cross-linking form polymer, while ensureing the cohesive force of composite material, improve composite material flow leveling and
Paintability, and it is environmentally protective.
(2) high containing rosin in the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer prepared by the present invention
A small amount of microballoon is added in composite material by molecule microballoon, is further increased the paintability and weatherability of adhesive, is reduced
Influence of the environment to viscosity, and rosin polymer microsphere surface contains carboxyl, can form microballoon with polymerizable acrylic monomer, contain
Some gelatin are more advantageous to be disperseed in modified gelatin acrylic resin compound material, is advantageously implemented the stabilization of binder performance
It is uniform, and microballoon has good adsorption capacity, is conducive to the absorption fastness for improving adhesive to timber.
(3) preparation method of the present invention is simple, and the material of selection is mostly that gelatin, rosin etc. are cheap, abundance, to ring
The material of border close friend, adhesive are good to the bond properties of timber, and spreadability is good, and viscosity is protected from environmental small.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
(1) gelatin that 5 parts of molecular mass is 4-8 ten thousand is added in 500 parts of distilled water, is passed through nitrogen and condensed water,
Heating water bath stirs 30min to 60 DEG C, and cooled to room temperature obtains gelatin solution.
(2) by 100 parts of rosin glycidyl methacrylate carboxylate be slowly added to 15 parts of methyl acrylate with
10 parts of N hydroxymethyl acrylamide, 300 parts of gelatin solutions continue to stir 30min, drip the potassium peroxydisulfate initiator of 5 parts of 10wt%
The sodium hydroxide solution of solution and 10 parts of 30wt%, 1h are added dropwise, warm water washing, filtering, the dry 12h in 40 DEG C of baking ovens
Obtain rosin polymer microballoon.
(3) gelatin solution of 100 parts of 10wt% is equipped in the reaction kettle of condensing unit, 3 parts of nitrous acid is added, are stirred at 0 DEG C
40min is mixed, 20min is vacuumized, adds 15 parts of methyl acrylate and 10 parts of N hydroxymethyl acrylamide, mass fraction, which is added, is
30% sodium hydroxide solution adjusts pH to 6.5, adds rosin polymer microballoon, stirring rod speed of agitator 100-120r/
It is warming up to 75 DEG C under min, the potassium peroxydisulfate initiator solution of 20 parts of 10wt% is added dropwise, 1h is added dropwise, then is warming up to 80 DEG C, protects
Temperature stops heating after reacting 1h, and the sodium hydroxide solution of 30wt% is added, and adjusts pH to 6.5, stops adding after insulation reaction 0.5h
Heat is cooled to 40 DEG C, obtains the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer, wherein rosin polymer is micro-
The mass fraction of ball is 5%.
Embodiment 2：
(1) gelatin that 10 parts of molecular mass is 4-8 ten thousand is added in 500 parts of distilled water, is passed through nitrogen and condensed water,
Heating water bath stirs 60min to 80 DEG C, and cooled to room temperature obtains gelatin solution.
(2) by 100 parts of rosin glycidyl methacrylate carboxylate be slowly added to 20 parts of methyl acrylate with
10 parts of N hydroxymethyl acrylamide, 300 parts of gelatin solutions continue to stir 60min, and the potassium peroxydisulfate that 5 parts of 10wt% are added dropwise causes
The sodium hydroxide solution of agent solution and 10 parts of 30wt%, 3h are added dropwise, warm water washing, and filtering is dry in 50 DEG C of baking ovens
12h obtains rosin polymer microballoon.
(3) gelatin solution of 100 parts of 15wt% is equipped in the reaction kettle of condensing unit, 4 parts of nitrous acid is added, are stirred at 5 DEG C
60min is mixed, 20min is vacuumized, adds 15 parts of methyl acrylate and 10 parts of N hydroxymethyl acrylamide, mass fraction, which is added, is
30% sodium hydroxide solution adjusts pH to 6.5, adds rosin polymer microballoon, under stirring rod speed of agitator 120r/min
75 DEG C are warming up to, the potassium peroxydisulfate initiator solution of 25 parts of 10wt% is added dropwise, 2h is added dropwise, then is warming up to 85 DEG C, and heat preservation is anti-
Stop heating after answering 1.5h, the sodium hydroxide solution of 30wt% is added, adjusts pH to 6.5, stop heating, drop after insulation reaction 1h
Temperature obtains the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer to 40 DEG C, wherein rosin polymer microballoon
Mass fraction is 25%.
Embodiment 3：
(1) gelatin that 8 parts of molecular mass is 4-8 ten thousand is added in 500 parts of distilled water, is passed through nitrogen and condensed water,
Heating water bath stirs 40min to 70 DEG C, and cooled to room temperature obtains gelatin solution.
(2) 100 parts of rosin glycidyl methacrylate carboxylate is slowly added to 18 parts of methyl acrylate and 9
The N hydroxymethyl acrylamide, 300 parts of gelatin solutions of part continue to stir 50min, the potassium peroxydisulfate initiator of 3 parts of 10wt% are added dropwise
The sodium hydroxide solution of solution and 8 parts of 30wt%, 2h are added dropwise, warm water washing, filtering, the dry 12h in 45 DEG C of baking ovens
Obtain rosin polymer microballoon.
(3) gelatin solution of 100 parts of 13wt% is equipped in the reaction kettle of condensing unit, 5 parts of nitrous acid is added, are stirred at 2 DEG C
50min is mixed, 20min is vacuumized, adds 20 parts of methyl acrylate and 10 parts of N hydroxymethyl acrylamide, mass fraction, which is added, is
30% sodium hydroxide solution adjusts pH to 6.5, adds rosin polymer microballoon, under stirring rod speed of agitator 110r/min
75 DEG C are warming up to, the potassium peroxydisulfate initiator solution of 23 parts of 10wt% is added dropwise, 3h is added dropwise, then is warming up to 90 DEG C, and heat preservation is anti-
Stop heating after answering 1.5h, the sodium hydroxide solution of 30wt% is added, adjusts pH to 6.5, stop heating, drop after insulation reaction 1h
Temperature obtains the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer to 40 DEG C, wherein rosin polymer microballoon
Mass fraction is 10%.
Embodiment 4：
(1) gelatin that 7 parts of molecular mass is 4-8 ten thousand is added in 500 parts of distilled water, is passed through nitrogen and condensed water,
Heating water bath stirs 55min to 75 DEG C, and cooled to room temperature obtains gelatin solution.
(2) by 100 parts of rosin glycidyl methacrylate carboxylate be slowly added to 18 parts of methyl acrylate with
10 parts of N hydroxymethyl acrylamide, 300 parts of gelatin solutions continue to stir 40min, and the potassium peroxydisulfate that 4 parts of 10wt% are added dropwise causes
The sodium hydroxide solution of agent solution and 8 parts of 30wt%, 1-3h are added dropwise, warm water washing, and filtering is dry in 44 DEG C of baking ovens
12h obtains rosin polymer microballoon.
(3) gelatin solution of 100 parts of 12wt% is equipped in the reaction kettle of condensing unit, 3 parts of nitrous acid is added, are stirred at 1 DEG C
45min is mixed, 20min is vacuumized, adds 18 parts of methyl acrylate and 9 parts of N hydroxymethyl acrylamide, mass fraction, which is added, is
30% sodium hydroxide solution adjusts pH to 7, adds rosin polymer microballoon, risen under stirring rod speed of agitator 120r/min
To 75 DEG C the potassium peroxydisulfate initiator solution of 25 parts of 10wt% is added dropwise, 2h is added dropwise, then is warming up to 90 DEG C, insulation reaction in temperature
Stop heating after 1.5h, the sodium hydroxide solution of 30wt% is added, adjusts pH to 6.5, stop heating, drop after insulation reaction 0.5h
Temperature obtains the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer to 45 DEG C, wherein rosin polymer microballoon
Mass fraction is 15%.
Embodiment 5：
(1) gelatin that 9 parts of molecular mass is 4-8 ten thousand is added in 500 parts of distilled water, is passed through nitrogen and condensed water,
Heating water bath stirs 60min to 80 DEG C, and cooled to room temperature obtains gelatin solution.
(2) 100 parts of rosin glycidyl methacrylate carboxylate is slowly added to 20 parts of methyl acrylate and 9
The N hydroxymethyl acrylamide, 300 parts of gelatin solutions of part continue to stir 50min, the potassium peroxydisulfate initiator of 3 parts of 10wt% are added dropwise
The sodium hydroxide solution of solution and 7 parts of 30wt%, 1-3h are added dropwise, warm water washing, and filtering is dry in 50 DEG C of baking ovens
12h obtains rosin polymer microballoon.
(3) gelatin solution of 100 parts of 10wt% is equipped in the reaction kettle of condensing unit, 4 parts of nitrous acid is added, are stirred at 3 DEG C
45min is mixed, 20min is vacuumized, adds 15 parts of methyl acrylate and 10 parts of N hydroxymethyl acrylamide, mass fraction, which is added, is
30% sodium hydroxide solution adjusts pH to 7, adds rosin polymer microballoon, stirring rod speed of agitator 100-120r/min
Under be warming up to 75 DEG C, the potassium peroxydisulfate initiator solution of 20 parts of 10wt% is added dropwise, 2h is added dropwise, then is warming up to 85 DEG C, heat preservation
Stop heating after reacting 1h, the sodium hydroxide solution of 30wt% is added, adjusts pH to 6.5, stop heating, drop after insulation reaction 1h
Temperature obtains the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer to 40 DEG C, wherein rosin polymer microballoon
Mass fraction is 20%.
Embodiment 6：
(1) gelatin that 10 parts of molecular mass is 4-8 ten thousand is added in 500 parts of distilled water, is passed through nitrogen and condensed water,
Heating water bath stirs 60min to 60 DEG C, and cooled to room temperature obtains gelatin solution.
(2) by 100 parts of rosin glycidyl methacrylate carboxylate be slowly added to 20 parts of methyl acrylate with
10 parts of N hydroxymethyl acrylamide, 300 parts of gelatin solutions continue to stir 55min, and the potassium peroxydisulfate that 5 parts of 10wt% are added dropwise causes
The sodium hydroxide solution of agent solution and 5 parts of 30wt%, 1-3h are added dropwise, warm water washing, and filtering is dry in 50 DEG C of baking ovens
12h obtains rosin polymer microballoon.
(3) gelatin solution of 100 parts of 15wt% is equipped in the reaction kettle of condensing unit, 5 parts of nitrous acid is added, are stirred at 5 DEG C
40min is mixed, 20min is vacuumized, adds 20 parts of methyl acrylate and 10 parts of N hydroxymethyl acrylamide, mass fraction, which is added, is
30% sodium hydroxide solution adjusts pH to 6.5, adds rosin polymer microballoon, stirring rod speed of agitator 100-120r/
It is warming up to 80 DEG C under min, the potassium peroxydisulfate initiator solution of 20 parts of 10wt% is added dropwise, 3h is added dropwise, then is warming up to 90 DEG C, protects
Stop heating after temperature reaction 1.5h, the sodium hydroxide solution of 30wt% be added, adjusts pH to 7, stop heating after insulation reaction 1h,
45 DEG C are cooled to, the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer, wherein rosin polymer microballoon are obtained
Mass fraction be 16%.
By the modified gelatin acrylic resin adhesive of the embodiment 1-6 microballoons containing rosin polymer prepared according to glue-spread
Subject to 250g/m2, gluing experiment is carried out to three-ply board, silent digestion time is 15min, is then fixed and is added with tongs both ends
It after pressing 2h, is dried under baking oven, after testing the shear strength of dry state and hygrometric state, Stratified stability and freeze-thaw stability and dielectric
The result of stability is as follows：
As seen from the above table, the machine of the modified gelatin acrylic resin adhesive for the microballoon containing rosin polymer that prepared by the present invention
Tool performance significantly improves, and stability is good, reduction protected from environmental.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of modified gelatin acrylic resin adhesive of microballoon containing rosin polymer, it is characterised in that：It is described high containing rosin
The modified gelatin acrylic resin adhesive of molecule microballoon includes rosin polymer microballoon and modified gelatin acrylic composite,
The rosin polymer microballoon includes rosin, gelatin and acrylate copolymer, the modified gelatin acrylic composite by
Gelatin is crosslinked to obtain with methyl acrylate, N hydroxymethyl acrylamide, and the modified gelatin acrylic resin adhesive is containing solid
Amount is 45% light gray microemulsion thick liquid, viscosity 200-300mPas.
2. a kind of modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 1, special
Sign is that the preparation method of the modified gelatin acrylic composite is：The gelatin solution of 100 parts of 10-15wt% is equipped with cold
In the reaction kettle of solidifying device, 3-5 parts of nitrous acid are added, stirs 40-60min at 0-5 DEG C, vacuumizes 20min, add 25-30 parts third
The sodium hydroxide solution that mass fraction is 30% is added in diluted acid class monomer mixture, adjusts pH to 6.5-7, and stirring rod stirring turns
It is warming up to 75-85 DEG C under fast 100-120r/min, the potassium peroxydisulfate initiator solution of 20-25 parts of 10wt% is added dropwise, 1-3h is added dropwise
It finishes, then is warming up to 80-90 DEG C, stop heating after insulation reaction 1-1.5h, the sodium hydroxide solution of 30wt% is added, adjust pH
To 6.5-7, stops heating after insulation reaction 0.5h, be cooled to 40-45 DEG C, obtain modified gelatin acrylic composite.
3. a kind of preparation method of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer, which is characterized in that packet
Include following steps：
(1) 5-10 parts of gelatin is added in 500 parts of distilled water, is passed through nitrogen and condensed water, heating water bath to 60-80 DEG C,
30-60min is stirred, cooled to room temperature obtains gelatin solution；
(2) the propylene acrylic monomer that 100 parts of rosin glycidyl methacrylate carboxylate is slowly added to 25-30 parts mixes
Object and 300 parts of gelatin solutions are closed, continues to stir 30-60min, the potassium peroxydisulfate initiator solution and 5-10 of 2-5 parts of 10wt% is added dropwise
The sodium hydroxide solution of the 30wt% of part, 1-3h are added dropwise, and washing, filtering and drying obtains rosin polymer microballoon；
(3) gelatin solution of 100 parts of 10-15wt% is equipped in the reaction kettle of condensing unit, 3-5 parts of nitrous acid of addition, at 0-5 DEG C
40-60min is stirred, 20min is vacuumized, adds 25-30 parts of propylene acids monomer mixtures, the hydrogen-oxygen that mass fraction is 30% is added
Change sodium solution, adjusts pH to 6.5-7, add rosin polymer microballoon, heat up under stirring rod speed of agitator 100-120r/min
To 75-85 DEG C, the potassium peroxydisulfate initiator solution of 20-25 parts of 10wt% is added dropwise, 1-3h is added dropwise, then is warming up to 80-90 DEG C,
Stop heating after insulation reaction 1-1.5h, the sodium hydroxide solution of 30wt% is added, adjusts pH to 6.5-7, insulation reaction 0.5h
Stop heating afterwards, is cooled to 40-45 DEG C, obtains the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer.
4. a kind of preparation of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 3
Method, it is characterised in that：In the step (1), gelatin is the industrial gelatine of alkaline process manufacture, molecular mass 4-8 in gelatin solution
Ten thousand.
5. a kind of preparation of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 3
Method, it is characterised in that：In the step (2) or step (3), the propylene acids monomer mixture by methyl acrylate with
N hydroxymethyl acrylamide forms, and wherein the mass ratio of methyl acrylate and N hydroxymethyl acrylamide is 15-20:8-10.
6. a kind of preparation of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 3
Method, it is characterised in that：In the step (2), washs and cleaned for warm water.
7. a kind of preparation of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 3
Method, it is characterised in that：It is dry for the dry 12h in 40-50 DEG C of baking oven in the step (2).
8. a kind of preparation of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 3
Method, it is characterised in that：It is loose in the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer in the step (3)
The mass fraction of fragrant polymer microsphere is 5-25%.
9. a kind of preparation of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 3
Method, it is characterised in that：In the step (3), change in the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer
Property gelatin acrylic resin adhesive is the light gray microemulsion thick liquid that solid content is 45%, viscosity 200-300mPa
s。
10. a kind of system of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 3
Preparation Method, it is characterised in that：In the step (3), the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer is used
It is bonded in plank.
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| CN201710218160.7A CN106995681B (en) | 2017-04-05 | 2017-04-05 | A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101503612A (en) * | 2009-03-10 | 2009-08-12 | 南京航空航天大学 | Solvent type repair adhesive special for ancient Chinese ink cultural relics and preparation thereof |
| CN101766981A (en) * | 2010-01-13 | 2010-07-07 | 桂林理工大学 | Method for preparing polymer microsphere by utilizing rosin and crylic acid hydroxy ester |
| CN103214609A (en) * | 2013-05-03 | 2013-07-24 | 广西大学 | Preparation method of monodisperse rosinyl polymer microsphere |
| CN104262549A (en) * | 2014-09-14 | 2015-01-07 | 桂林理工大学 | Method for synthesizing polymeric microsphere by using rosin glycidyl methacrylate ester |
-
2017
- 2017-04-05 CN CN201710218160.7A patent/CN106995681B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503612A (en) * | 2009-03-10 | 2009-08-12 | 南京航空航天大学 | Solvent type repair adhesive special for ancient Chinese ink cultural relics and preparation thereof |
| CN101766981A (en) * | 2010-01-13 | 2010-07-07 | 桂林理工大学 | Method for preparing polymer microsphere by utilizing rosin and crylic acid hydroxy ester |
| CN103214609A (en) * | 2013-05-03 | 2013-07-24 | 广西大学 | Preparation method of monodisperse rosinyl polymer microsphere |
| CN104262549A (en) * | 2014-09-14 | 2015-01-07 | 桂林理工大学 | Method for synthesizing polymeric microsphere by using rosin glycidyl methacrylate ester |
Non-Patent Citations (1)
| Title |
|---|
| "surface properties and structural transformation behaviors of mPEG-Maleic rosin copolymer in water";Juying Zhou，et al.;《polymers》;20170921;1-13页 * |
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