CN109988529A - A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum - Google Patents
A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum Download PDFInfo
- Publication number
- CN109988529A CN109988529A CN201910135256.6A CN201910135256A CN109988529A CN 109988529 A CN109988529 A CN 109988529A CN 201910135256 A CN201910135256 A CN 201910135256A CN 109988529 A CN109988529 A CN 109988529A
- Authority
- CN
- China
- Prior art keywords
- water
- mixed
- polyvinyl acetate
- stirred
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
Abstract
The invention discloses a kind of preparation methods of water-resistant type polyvinyl acetate adiabatic gum, belong to technical field of polymer materials.According to parts by weight, it successively weighs: 50~80 parts of matrix lotions, 10~30 parts of additives, 3~5 parts of urases, 6~8 parts of urea, 2~8 parts of tackifying resins and 10~15 parts of water, matrix lotion and additive are mixed in blender, and tackifying resin is added into blender, and urase, urea and water, in temperature be 30~40 DEG C, under conditions of revolving speed is 300~320r/min, after being stirred 60~90min, water-resistant type polyvinyl acetate adiabatic gum is obtained.The resulting water-resistant type polyvinyl acetate adiabatic gum of the present invention has excellent waterproof performance, and heat-proof quality is preferable, has very vast market prospect.
Description
Technical field
The invention discloses a kind of preparation methods of water-resistant type polyvinyl acetate adiabatic gum, belong to high polymer material technology
Field.
Background technique
Waterproof material, waterproof roll and water-repellent paint used in the flat roof of building for a long time, these waterproof materials
Fatal disadvantage is that the waterproof service life is short, only leakage infiltration just occurs within several years.The decades in service life of one building are to more than 100 years, light
The light maintenance overhaul of waterproof is done again must be tens times, cause trouble to the production and living of people, cause to national economy serious
Economic loss.Existing marine glue product can only do water-proof function, the service life is short, it is not ageing-resistant, not low temperature resistant, not heat-insulated, do not prevent
Fire.
" white glue with vinyl " is a kind of non-toxic and tasteless widely used polyvinyl acetate glue stick.Polyvinyl acetate
(Polyvinyl Acetate, PVAc) emulsion adhesive be using vinyl acetate (VAc) as reaction monomers in a dispersion medium
Through prepared by emulsion polymerization, also referred to as venamul is commonly called as white glue with vinyl or white glue, is yield in synthetic resin emulsion
One of maximum kind.Polyvinyl acetate emulsion adhesive has many advantages, such as: to porous material for example timber, paper,
Cotton, leather, ceramics etc. have very strong bonding force；Can room temperature curing, rate of drying is fast；Glue-line is colorless and transparent, does not pollute quilt
Viscous object；No pollution to the environment, it is safe and harmless；One pack system, easy to use, cleaning was easy, and storage period is longer, up to 1 year or more.But
It is this kind of adhesive the shortcomings that but there is water resistance and poor moisture resistances, is 65 010 and 96% suction in air in relative humidity
Wet rate is respectively 1.3% and 3.5%.In addition, its heat resistance is also to be improved.Pass through the sides such as copolymerization, blending, addition protecting colloid
Method can improve its service performance to a certain extent, expand application range.Currently, polyvinyl acetate emulsion adhesive has been used
In timber processing, cigarette manufacture, adhering fabric, furniture, printing bookbinding, paper-plastic stick, the manufacture of lamination cardboard box, label patch
The fields such as label, carpet backing, building decoration.Compared to solvent-based adhesive, polyvinyl acetate glue stick has at low cost, poly-
Close the advantage of simple process, safety and environmental protection, energy conservation green.But the poor water resistance of one pack system polyvinyl acetate emulsion, damp and hot
Under the conditions of, adhesive strength can decline to a great extent；Creep-resistant property is poor, and long-time electrostatic charge acts on lower adhesive and can slide；
Meanwhile it moisture-proof, cold resistance and mechanical stability it is also poor.This is greatly limited its application.
Currently, common esters of acrylic acid soft monomer and vinyl acetate copolymerized, esters of acrylic acid soft monomer and vinyl acetate
Polymer glass temperature can be reduced after ester copolymerization, improving its cold resistance, flexibility and moisture-proof addition crosslinking agent can mention
The adhesive strength and cohesive force of high lotion.Fumed silica is commonly called as white carbon black, is that the halide of silicon generates after pyrohydrolysis
With surface hydroxyl and adsorb water nano silica, it is non-toxic and tasteless, in macromolecular contain a large amount of free hydroxyl groups, in conjunction with
The physical characteristic of the specific surface area of the extra small partial size of nanoparticle and super large, the unsaturated bond for making it that can be deep into macromolecular chain are attached
Closely, and with the electron cloud of unsaturated bond it has an effect, the comprehensive functions such as its three-dimensional masonry structure, unsaturated ligancy in addition make
It can form space network with stronger adsorption capacity in conjunction with macromolecular chain, therefore polyvinyl acetate can be improved
The basic performances such as compactness, homogeneity, tensile strength, the waterproof and moisture permeability of ester film, but thermal insulation can not improve.
Based on the deficiencies of the prior art, developing one kind has heat-proof quality, and the preferable water-resistant type poly-vinegar acid of waterproof performance
Vinyl acetate adiabatic gum has preferable market prospects.
Summary of the invention
The present invention solves the technical problem of: it is poor for traditional polyvinyl acetate water-borne heat-insulating glue water resistance,
And heat-proof quality the problem of can not further increasing, provide a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum, it is specific the preparation method comprises the following steps:
(1) cornstarch is mixed with water 1:3~1:5 in mass ratio, and 0.2~0.3 times of cornstarch quality of emulsification is added
Agent and 0.1~0.3 times of cornstarch quality of epoxychloropropane are stirred to react after adjusting pH, obtain cross-linked corn starch dispersion
Liquid；
(2) cross-linked corn starch dispersion liquid is mixed with polyvinyl alcohol 4:1~5:1 in mass ratio, and cross-linked corn starch is added
The sodium bicarbonate of 0.05~0.10 times of the defoaming agent and cross-linked corn starch dispersion liquid quality that 0.05~0.08 times of dispersion liquid quality, is stirred
After mixing mixing, cross-linked corn starch mixed liquor is obtained, by cross-linked corn starch mixed liquor and initiator 12:1~18:1 in mass ratio
Mixing, and the vinylacetate of 0.3~0.4 times of cross-linked corn starch mixed liquor quality is added, after being stirred to react, obtain matrix cream
Liquid；
(3) potassium tetratitanate powder is mixed with calcium chloride mixed solution 1:3~1:5 in mass ratio, after microwave reaction, filters, does
It is dry, potassium tetratitanate powder must be pre-processed, pretreatment potassium tetratitanate powder is mixed with dopamine solution 1:8~1:10 in mass ratio
It closes, after being stirred to react, filters, it is dry, obtain modified potassium tetratitanate powder；
(4) modified potassium tetratitanate powder is mixed with treatment fluid 1:8~1:10 in mass ratio, after being stirred to react, is filtered, it is dry,
Obtain additive；
(5) according to parts by weight, it successively weighs: 50~80 parts of matrix lotions, 10~30 parts of additives, 3~5 parts of urases, 6~8
Part urea, 2~8 parts of tackifying resins and 10~15 parts of water, matrix lotion are mixed with additive, and tackifying resin is added, urase,
Urea and water, are stirred, and obtain water-resistant type polyvinyl acetate adiabatic gum.
Step (1) emulsifier is emulsifier op-10, any one in Arlacel-80 or Tween-60.
Step (2) defoaming agent is any one in methyl-silicone oil or dimethyl silicone polymer.
Step (2) initiator is potassium peroxydisulfate, any one in sodium peroxydisulfate or ammonium persulfate.
Step (3) the potassium tetratitanate powder is that 1.5:4.0 is mixed in molar ratio with titanium dioxide by potassium carbonate, grinding,
Calcining is washed, dry, obtains potassium tetratitanate powder.
Step (3) the calcium chloride mixed solution is to mix calcium chloride with water 1:5~1:8 in mass ratio, and chlorine is added
The lauryl amine for changing 0.01~0.06 times of calcareous amount, is stirred, and obtains calcium chloride mixed solution.
Step (4) treatment fluid be lignin sulfonic acid sodium solution is mixed with formaldehyde 25:1~30:1 in mass ratio, and
2~3 times of formaldehyde quality of sodium sulfite is added, after being stirred to react, lignin sulfonic acid sodium solution must be pre-processed, will be pre-processed wooden
Plain sodium sulfonate solution is mixed with potassium iodide 90:1~110:1 in mass ratio, and pretreatment sodium lignin sulfonate solution quality is added
0.1~0.2 times of 1,6- dibromo-hexane after being stirred to react under alkaline condition, obtains processing agent composition, will handle agent composition
Extraction, filtering, obtains treatment fluid.
Step (5) tackifying resin is any one in terpene resin or C9 Petropols.
The short fibre of 0.08~0.12 times of cross-linked corn starch mixed liquor quality can be added in step (2) described matrix lotion
Dimension, the staple fiber are terylene short fiber, any one in acrylic staples or polypropene staple.
The beneficial effects of the present invention are:
1.(1) modified potassium tetratitanate powder is added when preparing water-resistant type polyvinyl acetate adiabatic gum in additive by the present invention
End, and urea and urase is added in the product simultaneously, firstly, potassium tetratitanate powder is lamellar structure, it can after being added in product
Intermolecular binding force, the presence in reduction crack and aperture in product after product solidifies are improved, while one layer of waterproof layer can be formed,
The quantity of less prod inner via hole, and then the waterproofness of product is improved, secondly, potassium tetratitanate powder is passing through modification
Afterwards, lauryl amine and calcium ion can be inserted between the interlayer structure of potassium tetratitanate, the lauryl amine of insertion can widen the layer of potassium tetratitanate
Spacing, and improve the hydrophobic performance of potassium tetratitanate, and then interiors of products can be made to form certain air after being added in product
Layer, improves the heat-proof quality of product, also, the calcium ion that contains of potassium tetratitanate interlayer can after product use, in water by
Sodium ion displacement, forms free calcium ion, after being mixed with the carbanion of the urea being added in product and urase formation,
Precipitation of calcium carbonate can be formed, to further increase the consistency after product solidifies, improves the water resistance of product；
(2) present invention is handled with treatment fluid when preparing water-resistant type polyvinyl acetate adiabatic gum and is modified potassium tetratitanate powder, and one
Aspect, treatment fluid can generate after mixing with modified potassium tetratitanate powder with the amino of modified potassium tetratitanate powder adsorption
Reaction, to make to be coated on modified potassium tetratitanate powder table through the modified sodium lignin sulfonate of 1,6- dibromo-hexane in treatment fluid
Face, while the hydrophobic side having through the modified sodium lignin sulfonate of 1,6- dibromo-hexane being made to spread in the outside of potassium tetratitanate, into
And the waterproofness of product can be made to further increase, and on the other hand, the lignin sulfonic acid being modified in treatment fluid through 1,6- dibromo-hexane
Sodium has three-dimensional net structure, complicated cross-linked network can be formed between matrix, and then further increase the waterproofness of product,
Also, the presence and sulfonic acid group due to three-dimensional crosslinked network have certain suction-operated to calcium ion, can will produce
Raw precipitation of calcium carbonate is adsorbed in three-dimensional net structure, so that the intensity after solidifying product further increases, consistency into
One step improves, and then further increases the waterproofness of product, finally, with the loss of moisture when product solidifies, in treatment fluid
Modified sodium lignosulfonate can autohemagglutination formed tiny balloon, so that the thermal insulation of product be made to further increase.
Specific embodiment
The lignin sulfonic acid sodium solution that mass fraction is 10~12% is mixed in burning with formaldehyde 25:1~30:1 in mass ratio
In cup, and 2~3 times of formaldehyde quality of sodium sulfite is added into beaker, is 90~95 DEG C in temperature, revolving speed is 300~320r/
After being stirred to react 2~3h under conditions of min, lignin sulfonic acid sodium solution must be pre-processed, lignin sulfonic acid sodium solution will be pre-processed
It is mixed in three-necked flask with potassium iodide 90:1~110:1 in mass ratio, and pretreatment sulfomethylated lignin is added into three-necked flask
0.1~0.2 times of acid sodium solution quality of 1,6- dibromo-hexane, the addition rate of control 1,6- dibromo-hexane are 3~6mL/min,
The pH for controlling material in three-necked flask simultaneously is 11.0~11.5, and is 80~85 DEG C in temperature, and revolving speed is 230~350r/min
Under conditions of be stirred to react 4~5h after, obtain processing agent composition, will processing agent composition with after petroleum ether extraction 2~3 times, mistake
Filter, obtains treatment fluid；By potassium carbonate, 1.5:4.0 is mixed in grinder in molar ratio with titanium dioxide, 20~28h of mixed grinding,
Mixed-powder is obtained, under conditions of being 700~850 DEG C in temperature by mixed-powder after 2~3h of calcining at constant temperature, obtains potassium tetratitanate powder
Potassium tetratitanate powder batch mass fraction is by blank 10~20% salt acid elution for 8~12 times, and in temperature be 80~90
Under conditions of DEG C after dry 1~2h, potassium tetratitanate powder is obtained；Cornstarch and water 1:3~1:5 in mass ratio are mixed in three mouthfuls
In flask, and into three-necked flask be added 0.2~0.3 times of cornstarch quality emulsifier and cornstarch quality 0.1~0.3
Times epoxychloropropane, with mass fraction be 2~10% sodium hydroxide solution adjust three-necked flask in material pH to 11~
12, and be 90~95 DEG C in temperature, under conditions of revolving speed is 250~320r/min, after being stirred to react 1~2h, obtain cross-linked corn
Starch dispersion liquid；Cross-linked corn starch dispersion liquid and polyvinyl alcohol 4:1~5:1 in mass ratio are mixed in four-hole boiling flask, and
Defoaming agent and the cross-linked corn starch dispersion of 0.05~0.08 times of cross-linked corn starch dispersion liquid quality are added into four-hole boiling flask
The sodium bicarbonate that 0.05~0.10 times of liquid quality is 50~70 DEG C in temperature, under conditions of revolving speed is 250~320r/min, stirs
After mixing 20~30min, cross-linked corn starch mixed liquor is obtained, by cross-linked corn starch mixed liquor and initiator 12:1 in mass ratio
~18:1 mixing, and cross-linked corn starch mixed liquor quality is added into the mixture of cross-linked corn starch mixed liquor and initiator
0.3~0.4 times of vinylacetate, control vinylacetate addition rate be 2~6mL/min, in temperature be 90~95 DEG C,
Under conditions of revolving speed is 300~320r/min, after being stirred to react 30~60min, matrix lotion is obtained；By potassium tetratitanate powder and chlorine
Change calcium mixed solution 1:3~1:5 in mass ratio mixing, 1~2h of microwave reaction under conditions of microwave power is 400~600W
Afterwards, it filters, potassium tetratitanate powder batch must be pre-processed, the item for being 50~80 DEG C in temperature by pretreatment potassium tetratitanate powder batch
Under part after dry 1~2h, potassium tetratitanate powder must be pre-processed, is 10~15% by pretreatment potassium tetratitanate powder and mass fraction
Dopamine solution 1:8~1:10 in mass ratio mixing, in temperature be 30~50 DEG C, revolving speed be 200~300r/min condition
Under, after being stirred to react 30~50min, filtering obtains modified potassium tetratitanate powder batch, by modified potassium tetratitanate powder batch in temperature
Degree after dry 1~2h, obtains modified potassium tetratitanate powder under conditions of being 60~70 DEG C；It will modified potassium tetratitanate powder and treatment fluid
The mixing of 1:8~1:10 in mass ratio is 60~65 DEG C in temperature, under conditions of revolving speed is 300~450r/min, is stirred to react 1
After~3h, filtering obtains filter cake, under conditions of being 60~80 DEG C in temperature by filter cake after dry 1~2h, obtains additive；By weight
Number meter, successively weighs: 50~80 parts of matrix lotions, 10~30 parts of additives, 3~5 parts of urases, 6~8 parts of urea, and 2~8 parts
Matrix lotion and additive are mixed in blender by tackifying resin and 10~15 parts of water, and thickening tree is added into blender
Rouge, urase, urea and water are 30~40 DEG C in temperature, under conditions of revolving speed is 300~320r/min, it is stirred 60~
After 90min, water-resistant type polyvinyl acetate adiabatic gum is obtained.The emulsifier is emulsifier op-10, in Arlacel-80 or Tween-60
Any one.The defoaming agent is any one in methyl-silicone oil or dimethyl silicone polymer.The initiator is potassium peroxydisulfate,
Any one in sodium peroxydisulfate or ammonium persulfate.The calcium chloride mixed solution is by calcium chloride and water 1:5~1:8 in mass ratio
Mixing, and 0.01~0.06 times of calcium chloride quality of lauryl amine is added, it is stirred, obtains calcium chloride mixed solution.The thickening
Resin is any one in terpene resin or C9 Petropols.
Example 1
By mass fraction be 12% lignin sulfonic acid sodium solution and formaldehyde 30:1 in mass ratio be mixed in beaker, and to beaker
It is middle that 3 times of formaldehyde quality of sodium sulfite is added, in temperature be 95 DEG C, after revolving speed is stirred to react 3h under conditions of being 320r/min,
Lignin sulfonic acid sodium solution must be pre-processed, pretreatment lignin sulfonic acid sodium solution is mixed in potassium iodide 110:1 in mass ratio
In three-necked flask, and addition pre-processes 0.2 times of sodium lignin sulfonate solution quality of 1,6- dibromo-hexane, control into three-necked flask
The addition rate for making 1,6- dibromo-hexane is 6mL/min, while the pH for controlling material in three-necked flask is 11.5, and is in temperature
85 DEG C, after revolving speed is stirred to react 5h under conditions of being 350r/min, processing agent composition is obtained, agent composition petroleum ether will be handled
After extraction 3 times, filtering obtains treatment fluid；By potassium carbonate, 1.5:4.0 is mixed in grinder in molar ratio with titanium dioxide, mixing
28h is ground, mixed-powder is obtained, under conditions of being 850 DEG C in temperature by mixed-powder after calcining at constant temperature 3h, obtains potassium tetratitanate powder
Blank is done by salt acid elution 12 times that potassium tetratitanate powder batch mass fraction is 20%, and under the conditions of at a temperature of 90 °C
After dry 2h, potassium tetratitanate powder is obtained；Cornstarch and water 1:5 in mass ratio are mixed in three-necked flask, and to three-necked flask
0.3 times of cornstarch quality of emulsifier of middle addition and 0.3 times of cornstarch quality of epoxychloropropane are with mass fraction
10% sodium hydroxide solution adjusts the pH to 12 of material in three-necked flask, and is 95 DEG C in temperature, and revolving speed is the item of 320r/min
Under part, after being stirred to react 2h, cross-linked corn starch dispersion liquid is obtained；In mass ratio by cross-linked corn starch dispersion liquid and polyvinyl alcohol
5:1 is mixed in four-hole boiling flask, and into four-hole boiling flask be added 0.08 times of cross-linked corn starch dispersion liquid quality defoaming agent and
The sodium bicarbonate of 0.10 times of cross-linked corn starch dispersion liquid quality is 70 DEG C in temperature, under conditions of revolving speed is 320r/min, stirs
After mixing 30min, cross-linked corn starch mixed liquor is obtained, cross-linked corn starch mixed liquor and initiator 18:1 in mass ratio are mixed
It closes, and 0.4 times of cross-linked corn starch mixed liquor quality is added into the mixture of cross-linked corn starch mixed liquor and initiator
Vinylacetate, the addition rate for controlling vinylacetate is 6mL/min, is 95 DEG C in temperature, revolving speed is the item of 320r/min
Under part, after being stirred to react 60min, matrix lotion is obtained；Potassium tetratitanate powder and calcium chloride mixed solution 1:5 in mass ratio are mixed
It closes, under conditions of microwave power is 600W after microwave reaction 2h, filtering must pre-process potassium tetratitanate powder batch, will locate in advance
Under conditions of reason potassium tetratitanate powder batch is 80 DEG C in temperature after dry 2h, potassium tetratitanate powder must be pre-processed, will be pre-processed
Potassium tetratitanate powder is mixed with the dopamine solution 1:10 in mass ratio that mass fraction is 15%, is 50 DEG C in temperature, revolving speed is
Under conditions of 300r/min, after being stirred to react 50min, filtering obtains modified potassium tetratitanate powder batch, by modified potassium tetratitanate powder
Under conditions of last blank is 70 DEG C in temperature after dry 2h, modified potassium tetratitanate powder is obtained；It will modified potassium tetratitanate powder and place
Liquid 1:10 in mass ratio mixing is managed, is 65 DEG C in temperature, under conditions of revolving speed is 450r/min, after being stirred to react 3h, filtering is obtained
Filter cake obtains additive under conditions of being 80 DEG C in temperature by filter cake after dry 2h；According to parts by weight, it successively weighs: 80 parts of bases
Precursor emulsion, 30 parts of additives, 5 parts of urases, 8 parts of urea, 8 parts of tackifying resins and 15 parts of water mix matrix lotion with additive
In blender, and tackifying resin is added into blender, urase, urea and water, in temperature be 40 DEG C, revolving speed 320r/min
Under conditions of, after being stirred 90min, obtain water-resistant type polyvinyl acetate adiabatic gum.The emulsifier is emulsifier op-10.
The defoaming agent is methyl-silicone oil.The initiator is potassium peroxydisulfate.The calcium chloride mixed solution is to press calcium chloride and water
Mass ratio 1:5 mixing, and 0.06 times of calcium chloride quality of lauryl amine is added, it is stirred, obtains calcium chloride mixed solution.The increasing
Viscosity resin is terpene resin.
Example 2
By potassium carbonate, 1.5:4.0 is mixed in grinder in molar ratio with titanium dioxide, and mixed grinding 28h obtains mixed-powder, will
Under conditions of mixed-powder is 850 DEG C in temperature after calcining at constant temperature 3h, potassium tetratitanate powder batch is obtained, by potassium tetratitanate powder base
Material salt acid elution 12 times that mass fraction is 20%, and potassium tetratitanate powder is obtained after dry 2h under the conditions of at a temperature of 90 °C
End；Cornstarch and water 1:5 in mass ratio are mixed in three-necked flask, and cornstarch quality is added into three-necked flask
0.3 times of emulsifier and 0.3 times of cornstarch quality of epoxychloropropane, the sodium hydroxide solution tune for being 10% with mass fraction
Save three-necked flask in material pH to 12, and in temperature be 95 DEG C, revolving speed be 320r/min under conditions of, after being stirred to react 2h,
Obtain cross-linked corn starch dispersion liquid；Cross-linked corn starch dispersion liquid and polyvinyl alcohol 5:1 in mass ratio are mixed in four-hole boiling flask
In, and into four-hole boiling flask be added 0.08 times of cross-linked corn starch dispersion liquid quality defoaming agent and cross-linked corn starch dispersion liquid
The sodium bicarbonate that 0.10 times of quality is 70 DEG C in temperature, under conditions of revolving speed is 320r/min, after being stirred 30min, must be crosslinked
Cornstarch mixed liquor mixes cross-linked corn starch mixed liquor with initiator 18:1 in mass ratio, and to cross-linked corn starch
The vinylacetate of 0.4 times of cross-linked corn starch mixed liquor quality is added in the mixture of mixed liquor and initiator, controls acetic acid
The addition rate of vinyl acetate is 6mL/min, is 95 DEG C in temperature, under conditions of revolving speed is 320r/min, is stirred to react 60min
Afterwards, matrix lotion is obtained；Potassium tetratitanate powder is mixed with calcium chloride mixed solution 1:5 in mass ratio, in microwave power be 600W
Under conditions of after microwave reaction 2h, filtering must pre-process potassium tetratitanate powder batch, will pre-process potassium tetratitanate powder batch in
Temperature after dry 2h, must pre-process potassium tetratitanate powder under conditions of being 80 DEG C, by pretreatment potassium tetratitanate powder and quality point
It counts and is mixed for 15% dopamine solution 1:10 in mass ratio, be 50 DEG C in temperature, under conditions of revolving speed is 300r/min, stir
After reacting 50min, filtering obtains modified potassium tetratitanate powder batch, will modified potassium tetratitanate powder batch in temperature be 70 DEG C
Under the conditions of after dry 2h, obtain modified potassium tetratitanate powder to get additive；According to parts by weight, it successively weighs: 80 parts of matrix creams
Liquid, 30 parts of additives, 5 parts of urases, 8 parts of urea, 8 parts of tackifying resins and 15 parts of water, matrix lotion is mixed in additive and is stirred
It mixes in machine, and tackifying resin is added into blender, urase, urea and water are 40 DEG C in temperature, and revolving speed is the item of 320r/min
Under part, after being stirred 90min, water-resistant type polyvinyl acetate adiabatic gum is obtained.The emulsifier is emulsifier op-10.It is described
Defoaming agent is methyl-silicone oil.The initiator is potassium peroxydisulfate.The calcium chloride mixed solution is that calcium chloride and water are pressed quality
It is mixed than 1:5, and 0.06 times of calcium chloride quality of lauryl amine is added, be stirred, obtain calcium chloride mixed solution.The thickening tree
Rouge is terpene resin.
Example 3
By mass fraction be 12% lignin sulfonic acid sodium solution and formaldehyde 30:1 in mass ratio be mixed in beaker, and to beaker
It is middle that 3 times of formaldehyde quality of sodium sulfite is added, in temperature be 95 DEG C, after revolving speed is stirred to react 3h under conditions of being 320r/min,
Lignin sulfonic acid sodium solution must be pre-processed, pretreatment lignin sulfonic acid sodium solution is mixed in potassium iodide 110:1 in mass ratio
In three-necked flask, and addition pre-processes 0.2 times of sodium lignin sulfonate solution quality of 1,6- dibromo-hexane, control into three-necked flask
The addition rate for making 1,6- dibromo-hexane is 6mL/min, while the pH for controlling material in three-necked flask is 11.5, and is in temperature
85 DEG C, after revolving speed is stirred to react 5h under conditions of being 350r/min, processing agent composition is obtained, agent composition petroleum ether will be handled
After extraction 3 times, filtering obtains treatment fluid；By potassium carbonate, 1.5:4.0 is mixed in grinder in molar ratio with titanium dioxide, mixing
28h is ground, mixed-powder is obtained, under conditions of being 850 DEG C in temperature by mixed-powder after calcining at constant temperature 3h, obtains potassium tetratitanate powder
Blank is done by salt acid elution 12 times that potassium tetratitanate powder batch mass fraction is 20%, and under the conditions of at a temperature of 90 °C
After dry 2h, potassium tetratitanate powder is obtained；Cornstarch and water 1:5 in mass ratio are mixed in three-necked flask, and to three-necked flask
0.3 times of cornstarch quality of emulsifier of middle addition and 0.3 times of cornstarch quality of epoxychloropropane are with mass fraction
10% sodium hydroxide solution adjusts the pH to 12 of material in three-necked flask, and is 95 DEG C in temperature, and revolving speed is the item of 320r/min
Under part, after being stirred to react 2h, cross-linked corn starch dispersion liquid is obtained；In mass ratio by cross-linked corn starch dispersion liquid and polyvinyl alcohol
5:1 is mixed in four-hole boiling flask, and into four-hole boiling flask be added 0.08 times of cross-linked corn starch dispersion liquid quality defoaming agent and
The sodium bicarbonate of 0.10 times of cross-linked corn starch dispersion liquid quality is 70 DEG C in temperature, under conditions of revolving speed is 320r/min, stirs
After mixing 30min, cross-linked corn starch mixed liquor is obtained, cross-linked corn starch mixed liquor and initiator 18:1 in mass ratio are mixed
It closes, and 0.4 times of cross-linked corn starch mixed liquor quality is added into the mixture of cross-linked corn starch mixed liquor and initiator
Vinylacetate, the addition rate for controlling vinylacetate is 6mL/min, is 95 DEG C in temperature, revolving speed is the item of 320r/min
Under part, after being stirred to react 60min, matrix lotion is obtained；The dopamine solution that potassium tetratitanate powder and mass fraction are 15% is pressed into matter
Amount is mixed than 1:10, is 50 DEG C in temperature, under conditions of revolving speed is 300r/min, after being stirred to react 50min, filtering obtains modification
Potassium tetratitanate powder batch must be modified four under conditions of being 70 DEG C in temperature by modified potassium tetratitanate powder batch after dry 2h
Potassium titanate powder；Modified potassium tetratitanate powder is mixed with treatment fluid 1:10 in mass ratio, is 65 DEG C in temperature, revolving speed is
Under conditions of 450r/min, after being stirred to react 3h, filtering obtains filter cake, under conditions of being 80 DEG C in temperature by filter cake after dry 2h,
Obtain additive；According to parts by weight, it successively weighs: 80 parts of matrix lotions, 30 parts of additives, 5 parts of urases, 8 parts of urea, 8 parts of increasings
Matrix lotion and additive are mixed in blender, and tackifying resin are added into blender by viscosity resin and 15 parts of water, urea
Enzyme, urea and water are 40 DEG C in temperature, under conditions of revolving speed is 320r/min, after being stirred 90min, obtain water-resistant type poly-vinegar
Vinyl acetate adiabatic gum.The emulsifier is emulsifier op-10.The defoaming agent is methyl-silicone oil.The initiator is over cure
Sour potassium.The tackifying resin is terpene resin.
Example 4
By mass fraction be 12% lignin sulfonic acid sodium solution and formaldehyde 30:1 in mass ratio be mixed in beaker, and to beaker
It is middle that 3 times of formaldehyde quality of sodium sulfite is added, in temperature be 95 DEG C, after revolving speed is stirred to react 3h under conditions of being 320r/min,
Lignin sulfonic acid sodium solution must be pre-processed, pretreatment lignin sulfonic acid sodium solution is mixed in potassium iodide 110:1 in mass ratio
In three-necked flask, and addition pre-processes 0.2 times of sodium lignin sulfonate solution quality of 1,6- dibromo-hexane, control into three-necked flask
The addition rate for making 1,6- dibromo-hexane is 6mL/min, while the pH for controlling material in three-necked flask is 11.5, and is in temperature
85 DEG C, after revolving speed is stirred to react 5h under conditions of being 350r/min, processing agent composition is obtained, agent composition petroleum ether will be handled
After extraction 3 times, filtering obtains treatment fluid；By potassium carbonate, 1.5:4.0 is mixed in grinder in molar ratio with titanium dioxide, mixing
28h is ground, mixed-powder is obtained, under conditions of being 850 DEG C in temperature by mixed-powder after calcining at constant temperature 3h, obtains potassium tetratitanate powder
Blank is done by salt acid elution 12 times that potassium tetratitanate powder batch mass fraction is 20%, and under the conditions of at a temperature of 90 °C
After dry 2h, potassium tetratitanate powder is obtained；Cornstarch and water 1:5 in mass ratio are mixed in three-necked flask, and to three-necked flask
0.3 times of cornstarch quality of emulsifier of middle addition and 0.3 times of cornstarch quality of epoxychloropropane are with mass fraction
10% sodium hydroxide solution adjusts the pH to 12 of material in three-necked flask, and is 95 DEG C in temperature, and revolving speed is the item of 320r/min
Under part, after being stirred to react 2h, cross-linked corn starch dispersion liquid is obtained；In mass ratio by cross-linked corn starch dispersion liquid and polyvinyl alcohol
5:1 is mixed in four-hole boiling flask, and into four-hole boiling flask be added 0.08 times of cross-linked corn starch dispersion liquid quality defoaming agent and
The sodium bicarbonate of 0.10 times of cross-linked corn starch dispersion liquid quality is 70 DEG C in temperature, under conditions of revolving speed is 320r/min, stirs
After mixing 30min, cross-linked corn starch mixed liquor is obtained, cross-linked corn starch mixed liquor and initiator 18:1 in mass ratio are mixed
It closes, and 0.4 times of cross-linked corn starch mixed liquor quality is added into the mixture of cross-linked corn starch mixed liquor and initiator
Vinylacetate, the addition rate for controlling vinylacetate is 6mL/min, is 95 DEG C in temperature, revolving speed is the item of 320r/min
Under part, after being stirred to react 60min, matrix lotion is obtained；Potassium tetratitanate powder and calcium chloride mixed solution 1:5 in mass ratio are mixed
It closes, under conditions of microwave power is 600W after microwave reaction 2h, filtering must pre-process potassium tetratitanate powder batch, will locate in advance
Under conditions of reason potassium tetratitanate powder batch is 80 DEG C in temperature after dry 2h, potassium tetratitanate powder must be pre-processed；It will pretreatment
Potassium tetratitanate powder is mixed with treatment fluid 1:10 in mass ratio, is 65 DEG C in temperature, under conditions of revolving speed is 450r/min, is stirred
After reacting 3h, filtering obtains filter cake, under conditions of being 80 DEG C in temperature by filter cake after dry 2h, obtains additive；In parts by weight
Meter, successively weighs: 80 parts of matrix lotions, 30 parts of additives, 5 parts of urases, 8 parts of urea, 8 parts of tackifying resins and 15 parts of water, by base
Precursor emulsion and additive are mixed in blender, and tackifying resin is added into blender, urase, and urea and water are in temperature
40 DEG C, under conditions of revolving speed is 320r/min, after being stirred 90min, obtain water-resistant type polyvinyl acetate adiabatic gum.The cream
Agent is emulsifier op-10.The defoaming agent is methyl-silicone oil.The initiator is potassium peroxydisulfate.The calcium chloride mixing is molten
Liquid is to mix calcium chloride with water 1:5 in mass ratio, and 0.06 times of calcium chloride quality of lauryl amine is added, and is stirred, obtains chlorine
Change calcium mixed solution.The tackifying resin is terpene resin.
Comparative example: by potassium carbonate, 1.5:4.0 is mixed in grinder in molar ratio with titanium dioxide, and mixed grinding 28h is obtained
Mixed-powder obtains potassium tetratitanate powder batch, by four under conditions of being 850 DEG C in temperature by mixed-powder after calcining at constant temperature 3h
Potassium titanate powder blank mass fraction is salt acid elution 12 times of 20%, and is obtained after dry 2h under the conditions of at a temperature of 90 °C
Potassium tetratitanate powder；Cornstarch and water 1:5 in mass ratio are mixed in three-necked flask, and corn is added into three-necked flask
The emulsifier and 0.3 times of cornstarch quality of epoxychloropropane that 0.3 times of starch quality, the hydroxide for being 10% with mass fraction
Sodium solution adjusts the pH to 12 of material in three-necked flask, and is 95 DEG C in temperature, and under conditions of revolving speed is 320r/min, stirring is anti-
After answering 2h, cross-linked corn starch dispersion liquid is obtained；Cross-linked corn starch dispersion liquid and polyvinyl alcohol 5:1 in mass ratio are mixed in four
In mouthful flask, and the defoaming agent and cross-linked corn starch of 0.08 times of cross-linked corn starch dispersion liquid quality is added into four-hole boiling flask
The sodium bicarbonate that 0.10 times of dispersion liquid quality, in temperature be 70 DEG C, revolving speed be 320r/min under conditions of, after being stirred 30min,
Cross-linked corn starch mixed liquor is obtained, cross-linked corn starch mixed liquor is mixed with initiator 18:1 in mass ratio, and is beautiful to crosslinking
The vinylacetate of 0.4 times of cross-linked corn starch mixed liquor quality, control are added in the mixture of rice starch mixed liquor and initiator
The addition rate of preparing vinyl acetate ester is 6mL/min, is 95 DEG C in temperature, under conditions of revolving speed is 320r/min, is stirred to react
After 60min, matrix lotion is obtained；According to parts by weight, it successively weighs: 80 parts of matrix lotions, 30 parts of potassium tetratitanate powder, 5 parts of ureas
Matrix lotion and potassium tetratitanate powder are mixed in blender by enzyme, 8 parts of urea, 8 parts of tackifying resins and 15 parts of water, and to stirring
It mixes and tackifying resin is added in machine, urase, urea and water are 40 DEG C in temperature, under conditions of revolving speed is 320r/min, are stirred
After 90min, water-resistant type polyvinyl acetate adiabatic gum is obtained.The emulsifier is emulsifier op-10.The defoaming agent is methyl silicon
Oil.The initiator is potassium peroxydisulfate.The tackifying resin is terpene resin.
1 to 4 gained water-resistant type polyvinyl acetate adiabatic gum of example and comparative example product are subjected to performance detection, it is specific to examine
Survey method is as follows:
1. water absorption rate: 1 to 4 gained water-resistant type polyvinyl acetate adiabatic gum of example and comparative example product are tested by QJ990.9
Water absorption rate after for 24 hours；
2. thermal insulation: thermal coefficient detects test specimen referring to ASTM D5470；
Specific testing result is as shown in table 1:
Table 1: water absorption rate and thermal insulation performance detection table
By 1 testing result of table it is found that the resulting water-resistant type polyvinyl acetate adiabatic gum of the present invention has excellent waterproof performance,
And heat-proof quality is preferable.
Claims (9)
1. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum, which is characterized in that it is specific the preparation method comprises the following steps:
(1) cornstarch is mixed with water 1:3~1:5 in mass ratio, and 0.2~0.3 times of cornstarch quality of emulsification is added
Agent and 0.1~0.3 times of cornstarch quality of epoxychloropropane are stirred to react after adjusting pH, obtain cross-linked corn starch dispersion
Liquid；
(2) cross-linked corn starch dispersion liquid is mixed with polyvinyl alcohol 4:1~5:1 in mass ratio, and cross-linked corn starch is added
The sodium bicarbonate of 0.05~0.10 times of the defoaming agent and cross-linked corn starch dispersion liquid quality that 0.05~0.08 times of dispersion liquid quality, is stirred
After mixing mixing, cross-linked corn starch mixed liquor is obtained, by cross-linked corn starch mixed liquor and initiator 12:1~18:1 in mass ratio
Mixing, and the vinylacetate of 0.3~0.4 times of cross-linked corn starch mixed liquor quality is added, after being stirred to react, obtain matrix cream
Liquid；
(3) potassium tetratitanate powder is mixed with calcium chloride mixed solution 1:3~1:5 in mass ratio, after microwave reaction, filters, does
It is dry, potassium tetratitanate powder must be pre-processed, pretreatment potassium tetratitanate powder is mixed with dopamine solution 1:8~1:10 in mass ratio
It closes, after being stirred to react, filters, it is dry, obtain modified potassium tetratitanate powder；
(4) modified potassium tetratitanate powder is mixed with treatment fluid 1:8~1:10 in mass ratio, after being stirred to react, is filtered, it is dry,
Obtain additive；
(5) according to parts by weight, it successively weighs: 50~80 parts of matrix lotions, 10~30 parts of additives, 3~5 parts of urases, 6~8
Part urea, 2~8 parts of tackifying resins and 10~15 parts of water, matrix lotion are mixed with additive, and tackifying resin is added, urase,
Urea and water, are stirred, and obtain water-resistant type polyvinyl acetate adiabatic gum.
2. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum according to claim 1, it is characterised in that: step
Suddenly (1) described emulsifier is emulsifier op-10, any one in Arlacel-80 or Tween-60.
3. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum according to claim 1, it is characterised in that: step
Suddenly (2) described defoaming agent is any one in methyl-silicone oil or dimethyl silicone polymer.
4. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum according to claim 1, it is characterised in that: step
Suddenly (2) described initiator is potassium peroxydisulfate, any one in sodium peroxydisulfate or ammonium persulfate.
5. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum according to claim 1, it is characterised in that: step
Suddenly (3) described potassium tetratitanate powder is that 1.5:4.0 is mixed in molar ratio with titanium dioxide by potassium carbonate, is ground, and is calcined, washing,
It is dry, obtain potassium tetratitanate powder.
6. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum according to claim 1, it is characterised in that: step
Suddenly (3) described calcium chloride mixed solution is to mix calcium chloride with water 1:5~1:8 in mass ratio, and calcium chloride quality is added
0.01~0.06 times of lauryl amine, is stirred, and obtains calcium chloride mixed solution.
7. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum according to claim 1, it is characterised in that: step
Suddenly (4) described treatment fluid is to mix lignin sulfonic acid sodium solution with formaldehyde 25:1~30:1 in mass ratio, and formaldehyde matter is added
The sodium sulfite of 2~3 times of amount, after being stirred to react, must pre-process lignin sulfonic acid sodium solution, molten by sodium lignin sulfonate is pre-processed
Liquid is mixed with potassium iodide 90:1~110:1 in mass ratio, and 0.1~0.2 times of sodium lignin sulfonate solution quality of pretreatment is added
1,6- dibromo-hexane, after being stirred to react under alkaline condition, obtain processing agent composition, will processing agent composition extraction, filtering,
Obtain treatment fluid.
8. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum according to claim 1, it is characterised in that: step
Suddenly (5) described tackifying resin is any one in terpene resin or C9 Petropols.
9. a kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum according to claim 1, it is characterised in that step
Suddenly the staple fiber of 0.08~0.12 times of cross-linked corn starch mixed liquor quality, the short fibre can be added in (2) described matrix lotion
Tieing up is terylene short fiber, any one in acrylic staples or polypropene staple.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910135256.6A CN109988529A (en) | 2019-02-25 | 2019-02-25 | A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910135256.6A CN109988529A (en) | 2019-02-25 | 2019-02-25 | A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109988529A true CN109988529A (en) | 2019-07-09 |
Family
ID=67130356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910135256.6A Pending CN109988529A (en) | 2019-02-25 | 2019-02-25 | A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109988529A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111070804A (en) * | 2019-12-25 | 2020-04-28 | 上海诚格安全防护用品有限公司 | Heat insulation fabric and ultra-light portable heat insulation cloak |
| CN116987292A (en) * | 2023-06-26 | 2023-11-03 | 河南大树实业有限公司 | Preparation method of hollow sphere plastic pigment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634305A (en) * | 2012-04-23 | 2012-08-15 | 浙江农林大学 | Production method of starch-based formaldehyde-free glue |
| CN102732186A (en) * | 2012-07-12 | 2012-10-17 | 华东理工大学 | Modified starch adhesive and method for preparing same |
| CN106532390A (en) * | 2016-10-31 | 2017-03-22 | 阜阳市鼎铭汽车配件制造有限公司 | Surface-modified potassium titanate whisker-reinforced copper-based graphite motor carbon brush and preparation method thereof |
| US20180282588A1 (en) * | 2017-04-03 | 2018-10-04 | Eastman Chemical Company | Modified resins and uses thereof |
-
2019
- 2019-02-25 CN CN201910135256.6A patent/CN109988529A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634305A (en) * | 2012-04-23 | 2012-08-15 | 浙江农林大学 | Production method of starch-based formaldehyde-free glue |
| CN102732186A (en) * | 2012-07-12 | 2012-10-17 | 华东理工大学 | Modified starch adhesive and method for preparing same |
| CN106532390A (en) * | 2016-10-31 | 2017-03-22 | 阜阳市鼎铭汽车配件制造有限公司 | Surface-modified potassium titanate whisker-reinforced copper-based graphite motor carbon brush and preparation method thereof |
| US20180282588A1 (en) * | 2017-04-03 | 2018-10-04 | Eastman Chemical Company | Modified resins and uses thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111070804A (en) * | 2019-12-25 | 2020-04-28 | 上海诚格安全防护用品有限公司 | Heat insulation fabric and ultra-light portable heat insulation cloak |
| CN111070804B (en) * | 2019-12-25 | 2021-09-24 | 上海诚格安全防护用品有限公司 | Heat insulation fabric and ultra-light portable heat insulation cloak |
| CN116987292A (en) * | 2023-06-26 | 2023-11-03 | 河南大树实业有限公司 | Preparation method of hollow sphere plastic pigment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107163855B (en) | A kind of silica aerogel reflective insulation exterior wall paint and preparation method thereof | |
| CN103725051B (en) | A kind of body material of inorganic paint and application thereof | |
| CN104017413A (en) | Thermal insulation putty for internal walls and application method thereof | |
| CN107201159A (en) | A kind of cracking resistance, anti-dropout coating and preparation method | |
| CN109988529A (en) | A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum | |
| CN104073107A (en) | Textured paint | |
| CN102485820A (en) | White emulsion with environmental protection and high viscosity and its preparation method | |
| CN102040928A (en) | Modified waterproof frost-resisting white latex | |
| CN106520011B (en) | A kind of preparation method of water-fast polyurethane adhesive nano-calcium carbonate | |
| CN101220249A (en) | Green environment protection adhesion agent and production method | |
| CN104327658A (en) | Textured coating | |
| CN104109444A (en) | Biomass internal wall paint and preparation method thereof | |
| CN108342170A (en) | Aqueous, environmental protective glue for tile, preparation method and applications | |
| CN101648789A (en) | Light color clay and production method thereof | |
| CN103215825B (en) | Printing adhesive of stone paper wallpaper and preparation method of printing adhesive | |
| CN107572878B (en) | Heat-insulation fireproof stone-like coating and preparation method thereof | |
| CN108424738A (en) | A kind of preparation method of modified poly ethylene alcohol radical splicing adhesive | |
| CN103145913B (en) | Epoxy acrylate copolymer emulsion and preparation and use thereof in production of humidifying paint for internal wall | |
| CN102558420B (en) | Vinyl acetate copolymer modified by silsesquioxane (tris sulfonic acid isobutyl polyhedral oligomeric silsesquioxane (POSS)) and preparation method thereof | |
| CN106590118A (en) | Heat insulation and heat preservation coating for building external wall and preparation method thereof | |
| CN112521816A (en) | Medium and low brightness reflective heat insulation stone-like paint and preparation method thereof | |
| CN109575844A (en) | A kind of preparation method viscosifying water-resistant white latex | |
| CN114163881B (en) | Single-component ceramic tile back gluing composition and application thereof | |
| CN111849272A (en) | Sand coating and preparation method thereof | |
| CN104877063A (en) | Polyvinyl acetate emulsion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190709 |