CN106995681A - 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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- CN106995681A CN106995681A CN201710218160.7A CN201710218160A CN106995681A CN 106995681 A CN106995681 A CN 106995681A CN 201710218160 A CN201710218160 A CN 201710218160A CN 106995681 A CN106995681 A CN 106995681A
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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
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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 acid composite, rosin polymer microballoon includes rosin, gelatin and acrylate copolymer, and modified gelatin acrylic acid composite is obtained by gelatin with methyl acrylate, the crosslinking of N NMAs.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 generally that gelatin, rosin etc. are cheap, abundance, environment amenable material, contain two kinds of forms of microballoon and emulsion in adhesive, good to the bond properties of timber, spreadability is good, viscosity is protected from environmental small, and combination property is significantly improved.
Description
Technical field
The invention belongs to gelatin adhesive field of material technology, and in particular to a kind of modification of 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 up of 18 kinds of amino acid, the Amphiphatic high polymer polyelectrolyte with protein structure, with excellent biology drop
Performance is solved, low antigenic and good biocompatibility, gelatin solution also has unique performance in itself, at low temperature can shape
Into 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, it is not necessary to plus other auxiliary agents, but individually gelatin adhesive viscosity is big, it is not easy to
Brush coating and levelling, and easily moisture absorption mildew, viscosity are larger with environmental change.When temperature is increased to more than the freezing point of gelatin
When, gelatin molecule is with arbitrary curly presence, and in freezing point triple-helix structure formed below, gelatin also contains substantial amounts of dried meat ammonia
Chemical reaction and electrostatic interaction formation modified gelatin can occur with a variety of crosslinking agents for acid, hydroxy-proline and glycine, 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
Arrive.The bioadhesive has good bioactivity, preferable mechanical property, biodegradable and promotion moist environment group
The advantages of knitting healing.The disclosed composites being made up of acrylic copolymer and gelatin of Chinese patent CN 101555305A and
Its preparation method, GMA, acrylic acid are mixed with the copolymer of esters of acrylic acid with aqueous gelatin solution,
Heating stirring, it is well mixed to form composite.From above-mentioned prior art, by Macroscopic single crystals such as gelatin and acrylic acid
Composite adhesive has the advantages that environmentally friendly, nontoxic, degradable, but the stability of viscosity in adhesive, levelability and dry
Dry speed is all difficult to control to optimal.Rosin has larger molecular weight, there is 3 six-membered cyclic structures, is conducive to promoting to be combined
Adhesive has new structure and function.The content of the invention
The technical problem to be solved in the present invention is to provide a kind of modified gelatin acrylic resin of microballoon containing rosin polymer
Adhesive and preparation method thereof, rosin polymer microballoon is added in gelatin and acrylic monomers, by rosin polymer microballoon
The performance for wherein improving modified gelatin acrylic resin adhesive is incorporated, the bonding force to timber, levelling ability, reduction is improved
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 acid composite, and the rosin is high
Molecule microballoon includes rosin, gelatin and acrylate copolymer, and the modified gelatin acrylic acid composite is by gelatin and propylene
Sour methyl esters, N hydroxymethyl acrylamide crosslinking are obtained, and the modified gelatin acrylic resin adhesive is that solid content is 45%
Light gray microemulsion thick liquid, viscosity is 200-300mPas.
As the preferred of above-mentioned technical proposal, the preparation method of the modified gelatin acrylic acid composite is：By 100 parts
10-15wt% gelatin solution is equipped with the reactor of condensing unit, is added at 3-5 parts of nitrous acid, 0-5 DEG C and is stirred 40-60min,
20min, plus 25-30 parts of propylene acids monomer mixtures are vacuumized, the sodium hydroxide solution that mass fraction is 30%, regulation is added
75-85 DEG C is warming up under pH to 6.5-7, puddler speed of agitator 100-120r/min, 20-25 parts of 10wt% persulfuric acid is added dropwise
Potassium initiator solution, 1-3h completion of dropping, then stopping heating after 80-90 DEG C, insulation reaction 1-1.5h is warming up to, add 30wt%
Sodium hydroxide solution, adjust pH to 6.5-7, stop heating after insulation reaction 0.5h, be cooled to 40-45 DEG C, obtain being modified bright
Glue acrylic resin adhesive.
The present invention also provides a kind of preparation method of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer,
Comprise the following steps：
(1) in the distilled water that 5-10 parts of gelatin is added to 500 parts, nitrogen and condensed water, heating water bath to 60-80 are passed through
DEG C, 30-60min is stirred, room temperature is naturally cooled to, obtains gelatin solution；
(2) 100 parts of rosin GMA carboxylate is slowly added to 25-30 parts of propylene acrylic monomers
Mixture and 300 parts of gelatin solutions, continue to stir 30-60min, 2-5 parts of 10wt% potassium peroxydisulfate initiator solution and 5- are added dropwise
10 parts of 30wt% sodium hydroxide solution, 1-3h completion of dropping, washing, filtering and drying obtains rosin polymer microballoon；
(3) 100 parts of 10-15wt% gelatin solution is equipped with the reactor of condensing unit, adds 3-5 parts of nitrous acid, 0-5
40-60min is stirred at DEG C, 20min, plus 25-30 parts of propylene acids monomer mixtures are vacuumized, it is 30% to add mass fraction
Sodium hydroxide solution, pH is to 6.5-7 for regulation, adds under rosin polymer microballoon, puddler speed of agitator 100-120r/min
75-85 DEG C is warming up to, 20-25 parts of 10wt% potassium peroxydisulfate initiator solution, 1-3h completion of dropping is added dropwise, then be warming up to 80-
90 DEG C, stop heating after insulation reaction 1-1.5h, add 30wt% sodium hydroxide solution, adjust pH to 6.5-7, insulation reaction
Stop heating after 0.5h, be cooled to 40-45 DEG C, obtain the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer.
As the preferred of above-mentioned technical proposal, in the step (1), gelatin is that the woven industry of alkaline process is bright in gelatin solution
Glue, molecular mass is 4-8 ten thousand.
As the preferred of above-mentioned technical proposal, in the step (2) or step (3), the propylene acrylic monomer mixing
Thing is made up of methyl acrylate with N hydroxymethyl acrylamide, and the mass ratio of wherein acrylate and N hydroxymethyl acrylamide is
15-20:8-10。
As the preferred of above-mentioned technical proposal, in the step (2), wash and cleaned for warm water.
As the preferred of above-mentioned technical proposal, in the step (2), it is that 12h is dried in 40-50 DEG C of baking oven to dry.
As the preferred of above-mentioned technical proposal, 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 the preferred of above-mentioned technical proposal, 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 the preferred of above-mentioned technical proposal, 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, gelatin is after nitrite-oxidizing processing, and part hydrophile amino is transformed into hydroxyl, reduction
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 formation polymer, it is ensured that while the cohesive force of composite, improve composite flow leveling and
Paintability, and environmental protection.
(2) it is high containing rosin in the modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer prepared by the present invention
Molecule microballoon, a small amount of microballoon is added in composite, is further improved the paintability and weatherability of adhesive, is reduced
Influence of the environment to viscosity, and rosin polymer microsphere surface contains carboxyl, can contain with polymerizable acrylic monomer formation microballoon
Some gelatin are more beneficial for disperseing in modified gelatin acrylic resin compound material, are advantageously implemented the stabilization of binder performance
It is homogeneous, and microballoon has good adsorption capacity, is conducive to improving absorption fastness of the adhesive to timber.
(3) preparation method of the present invention is simple, and the material of selection is generally that gelatin, rosin etc. are cheap, abundance, to ring
The friendly material in border, adhesive is good to the bond properties of timber, and spreadability is good, and viscosity is protected from environmental small.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, 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) 5 parts of molecular mass is added in 500 parts of distilled water for 4-8 ten thousand gelatin, is passed through nitrogen and condensed water,
Heating water bath stirs 30min, naturally cools to room temperature, obtain gelatin solution to 60 DEG C.
(2) 100 parts of rosin GMA carboxylate is slowly added to 15 parts of acrylate and 10
The N hydroxymethyl acrylamide, 300 parts of gelatin solutions of part, continue to stir 30min, the potassium peroxydisulfate initiator for dripping 5 parts of 10wt% is molten
The sodium hydroxide solution of liquid and 10 parts of 30wt%, 1h completion of dropping, warm water washing, filtering, dry 12h is obtained in 40 DEG C of baking ovens
To rosin polymer microballoon.
(3) 100 parts of 10wt% gelatin solution is equipped with the reactor of condensing unit, adds and stirred at 3 parts of nitrous acid, 0 DEG C
40min is mixed, 20min, plus 15 parts of acrylate and 10 parts of N hydroxymethyl acrylamide is vacuumized, adding mass fraction is
30% sodium hydroxide solution, pH is to 6.5 for regulation, adds rosin polymer microballoon, puddler speed of agitator 100-120r/
75 DEG C are warming up under min, 20 parts of 10wt% potassium peroxydisulfate initiator solution, 1h completion of dropping is added dropwise, then be warming up to 80 DEG C, guarantor
Stopping heating after temperature reaction 1h, adds 30wt% sodium hydroxide solution, adjusts and stops adding after pH to 6.5, 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) 10 parts of molecular mass is added in 500 parts of distilled water for 4-8 ten thousand gelatin, is passed through nitrogen and condensed water,
Heating water bath stirs 60min, naturally cools to room temperature, obtain gelatin solution to 80 DEG C.
(2) 100 parts of rosin GMA carboxylate is slowly added to 20 parts of acrylate and 10
The N hydroxymethyl acrylamide, 300 parts of gelatin solutions of part, continue to stir 60min, 5 parts of 10wt% potassium peroxydisulfate initiator are added dropwise
12h is dried in the sodium hydroxide solution of solution and 10 parts of 30wt%, 3h completion of dropping, warm water washing, filtering in 50 DEG C of baking ovens
Obtain rosin polymer microballoon.
(3) 100 parts of 15wt% gelatin solution is equipped with the reactor of condensing unit, adds and stirred at 4 parts of nitrous acid, 5 DEG C
60min is mixed, 20min, plus 15 parts of acrylate and 10 parts of N hydroxymethyl acrylamide is vacuumized, adding mass fraction is
30% sodium hydroxide solution, pH is to 6.5 for regulation, adds under rosin polymer microballoon, puddler speed of agitator 120r/min
It is warming up to 75 DEG C, is added dropwise 25 parts of 10wt% potassium peroxydisulfate initiator solution, 2h completion of dropping, then be warming up to 85 DEG C, insulation is anti-
Answer and stop heating after 1.5h, add 30wt% sodium hydroxide solution, adjust and stop heating after pH to 6.5, insulation reaction 1h, drop
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) 8 parts of molecular mass is added in 500 parts of distilled water for 4-8 ten thousand gelatin, is passed through nitrogen and condensed water,
Heating water bath stirs 40min, naturally cools to room temperature, obtain gelatin solution to 70 DEG C.
(2) by 100 parts of rosin GMA carboxylate be slowly added to 18 parts acrylate and 9 parts
N hydroxymethyl acrylamide, 300 parts of gelatin solutions, continue stir 50min, be added dropwise 3 parts of 10wt% potassium peroxydisulfate initiator it is molten
The sodium hydroxide solution of liquid and 8 parts of 30wt%, 2h completion of dropping, warm water washing, filtering, dry 12h is obtained in 45 DEG C of baking ovens
To rosin polymer microballoon.
(3) 100 parts of 13wt% gelatin solution is equipped with the reactor of condensing unit, adds and stirred at 5 parts of nitrous acid, 2 DEG C
50min is mixed, 20min, plus 20 parts of acrylate and 10 parts of N hydroxymethyl acrylamide is vacuumized, adding mass fraction is
30% sodium hydroxide solution, pH is to 6.5 for regulation, adds under rosin polymer microballoon, puddler speed of agitator 110r/min
It is warming up to 75 DEG C, is added dropwise 23 parts of 10wt% potassium peroxydisulfate initiator solution, 3h completion of dropping, then be warming up to 90 DEG C, insulation is anti-
Answer and stop heating after 1.5h, add 30wt% sodium hydroxide solution, adjust and stop heating after pH to 6.5, insulation reaction 1h, drop
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) 7 parts of molecular mass is added in 500 parts of distilled water for 4-8 ten thousand gelatin, is passed through nitrogen and condensed water,
Heating water bath stirs 55min, naturally cools to room temperature, obtain gelatin solution to 75 DEG C.
(2) 100 parts of rosin GMA carboxylate is slowly added to 18 parts of acrylate and 10
The N hydroxymethyl acrylamide, 300 parts of gelatin solutions of part, continue to stir 40min, 4 parts of 10wt% potassium peroxydisulfate initiator are added dropwise
The sodium hydroxide solution of solution and 8 parts of 30wt%, 1-3h completion of dropping, warm water washing, filtering is dried in 44 DEG C of baking ovens
12h obtains rosin polymer microballoon.
(3) 100 parts of 12wt% gelatin solution is equipped with the reactor of condensing unit, adds and stirred at 3 parts of nitrous acid, 1 DEG C
45min is mixed, 20min, plus 18 parts of acrylate and 9 parts of N hydroxymethyl acrylamide is vacuumized, adding mass fraction is
30% sodium hydroxide solution, pH is to 7 for regulation, adds under rosin polymer microballoon, puddler speed of agitator 120r/min and rises
To 75 DEG C 25 parts of 10wt% potassium peroxydisulfate initiator solution, 2h completion of dropping is added dropwise, then be warming up to 90 DEG C, insulation reaction in temperature
Stop heating after 1.5h, add 30wt% sodium hydroxide solution, adjust and stop heating after pH to 6.5, insulation reaction 0.5h, drop
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) 9 parts of molecular mass is added in 500 parts of distilled water for 4-8 ten thousand gelatin, is passed through nitrogen and condensed water,
Heating water bath stirs 60min, naturally cools to room temperature, obtain gelatin solution to 80 DEG C.
(2) by 100 parts of rosin GMA carboxylate be slowly added to 20 parts acrylate and 9 parts
N hydroxymethyl acrylamide, 300 parts of gelatin solutions, continue stir 50min, be added dropwise 3 parts of 10wt% potassium peroxydisulfate initiator it is molten
12h is dried in the sodium hydroxide solution of liquid and 7 parts of 30wt%, 1-3h completion of dropping, warm water washing, filtering in 50 DEG C of baking ovens
Obtain rosin polymer microballoon.
(3) 100 parts of 10wt% gelatin solution is equipped with the reactor of condensing unit, adds and stirred at 4 parts of nitrous acid, 3 DEG C
45min is mixed, 20min, plus 15 parts of acrylate and 10 parts of N hydroxymethyl acrylamide is vacuumized, adding mass fraction is
30% sodium hydroxide solution, pH is to 7 for regulation, adds rosin polymer microballoon, puddler speed of agitator 100-120r/min
Under be warming up to 75 DEG C, 20 parts of 10wt% potassium peroxydisulfate initiator solution, 2h completion of dropping is added dropwise, then be warming up to 85 DEG C, insulation
React and stop heating after 1h, add 30wt% sodium hydroxide solution, adjust and stop heating after pH to 6.5, insulation reaction 1h, drop
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) 10 parts of molecular mass is added in 500 parts of distilled water for 4-8 ten thousand gelatin, is passed through nitrogen and condensed water,
Heating water bath stirs 60min, naturally cools to room temperature, obtain gelatin solution to 60 DEG C.
(2) 100 parts of rosin GMA carboxylate is slowly added to 20 parts of acrylate and 10
The N hydroxymethyl acrylamide, 300 parts of gelatin solutions of part, continue to stir 55min, 5 parts of 10wt% potassium peroxydisulfate initiator are added dropwise
The sodium hydroxide solution of solution and 5 parts of 30wt%, 1-3h completion of dropping, warm water washing, filtering is dried in 50 DEG C of baking ovens
12h obtains rosin polymer microballoon.
(3) 100 parts of 15wt% gelatin solution is equipped with the reactor of condensing unit, adds and stirred at 5 parts of nitrous acid, 5 DEG C
40min is mixed, 20min, plus 20 parts of acrylate and 10 parts of N hydroxymethyl acrylamide is vacuumized, adding mass fraction is
30% sodium hydroxide solution, pH is to 6.5 for regulation, adds rosin polymer microballoon, puddler speed of agitator 100-120r/
80 DEG C are warming up under min, 20 parts of 10wt% potassium peroxydisulfate initiator solution, 3h completion of dropping is added dropwise, then be warming up to 90 DEG C, guarantor
Stop heating after temperature reaction 1.5h, add 30wt% sodium hydroxide solution, adjust and stop heating after pH to 7, 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 is 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
It is defined for 250g/m2, gluing experiment is carried out to three-ply board, digestion time of remaining silent is 15min, is then fixed and added with tongs two ends
Press after 2h, dried under baking oven, after testing dry state and the shear strength of 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 of the microballoon containing rosin polymer prepared by the present invention
Tool performance is significantly improved, and stability is good, reduction protected from environmental.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into 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 acid composite,
The rosin polymer microballoon includes rosin, gelatin and acrylate copolymer, the modified gelatin acrylic acid composite by
Gelatin is obtained with methyl acrylate, N hydroxymethyl acrylamide crosslinking, and the modified gelatin acrylic resin adhesive is containing solid
The light gray microemulsion thick liquid for 45% is measured, viscosity is 200-300mPas.
2. a kind of modified gelatin acrylic resin adhesive of microballoon containing rosin polymer according to claim 1, it is special
Levy and be, the preparation method of the modified gelatin acrylic acid composite is：100 parts of 10-15wt% gelatin solution is equipped with cold
In the reactor of solidifying device, add at 3-5 parts of nitrous acid, 0-5 DEG C and stir 40-60min, vacuumize 20min, plus 25-30 parts third
Diluted acid class monomer mixture, adds the sodium hydroxide solution that mass fraction is 30%, adjusts pH to 6.5-7, and puddler stirring turns
75-85 DEG C is warming up under fast 100-120r/min, 20-25 parts of 10wt% potassium peroxydisulfate initiator solution is added dropwise, 1-3h is added dropwise
Finish, then be warming up to stopping heating after 80-90 DEG C, insulation reaction 1-1.5h, add 30wt% 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 gelatin acrylic resin adhesive.
3. a kind of preparation method of the modified gelatin acrylic resin adhesive of microballoon containing rosin polymer, it is characterised in that bag
Include following steps：
(1) in the distilled water that 5-10 parts of gelatin is added to 500 parts, nitrogen and condensed water are passed through, heating water bath to 60-80 DEG C,
30-60min is stirred, room temperature is naturally cooled to, obtains gelatin solution；
(2) the propylene acrylic monomer that 100 parts of rosin GMA carboxylate is slowly added into 25-30 parts is mixed
Compound and 300 parts of gelatin solutions, continue to stir 30-60min, 2-5 parts of 10wt% potassium peroxydisulfate initiator solution and 5-10 are added dropwise
The 30wt% of part sodium hydroxide solution, 1-3h completion of dropping, washing, filtering and drying obtains rosin polymer microballoon；
(3) 100 parts of 10-15wt% gelatin solution is equipped with the reactor of condensing unit, added at 3-5 parts of nitrous acid, 0-5 DEG C
40-60min is stirred, 20min, plus 25-30 parts of propylene acids monomer mixtures are vacuumized, the hydrogen-oxygen that mass fraction is 30% is added
Change sodium solution, pH is to 6.5-7 for regulation, add under rosin polymer microballoon, puddler speed of agitator 100-120r/min and heat up
To 75-85 DEG C, 20-25 parts of 10wt% potassium peroxydisulfate initiator solution, 1-3h completion of dropping is added dropwise, then is warming up to 80-90 DEG C,
Stop heating after insulation reaction 1-1.5h, add 30wt% sodium hydroxide solution, adjust pH to 6.5-7, insulation reaction 0.5h
Stop heating afterwards, be cooled to 40-45 DEG C, obtain 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 woven industrial gelatine of alkaline process in gelatin solution, and molecular mass is 4-8
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 is constituted, and wherein the mass ratio of 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), wash 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：In the step (2), it is that 12h is dried in 40-50 DEG C of baking oven to dry.
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%, and viscosity is 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
In plank bonding.
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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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113995444A (en) * | 2021-11-03 | 2022-02-01 | 深圳大学 | Hydrogel microneedle patch and preparation method and application thereof |
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| 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 |
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2017
- 2017-04-05 CN CN201710218160.7A patent/CN106995681B/en not_active Expired - Fee Related
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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 |
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| JUYING ZHOU，ET AL.: ""surface properties and structural transformation behaviors of mPEG-Maleic rosin copolymer in water"", 《POLYMERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113995444A (en) * | 2021-11-03 | 2022-02-01 | 深圳大学 | Hydrogel microneedle patch and preparation method and application thereof |
| CN113995444B (en) * | 2021-11-03 | 2024-05-07 | 深圳大学 | Hydrogel microneedle patch and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
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| CN106995681B (en) | 2018-09-18 |
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