CN108329881A - A kind of preparation method of weather-proof cloud stone glue - Google Patents
A kind of preparation method of weather-proof cloud stone glue Download PDFInfo
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- CN108329881A CN108329881A CN201810137275.8A CN201810137275A CN108329881A CN 108329881 A CN108329881 A CN 108329881A CN 201810137275 A CN201810137275 A CN 201810137275A CN 108329881 A CN108329881 A CN 108329881A
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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
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of preparation methods of weather-proof cloud stone glue, belong to stone material adhesive technical field.It counts in parts by weight, 120~150 parts of unsaturated polyester resins are weighed successively, 80~90 parts of fillers, 50~80 parts of epoxy acrylic resin mixtures, 50~70 parts of starch adhesives, 15~20 parts of polyallylamines, 12~18 parts of hydroxymethyl celluloses, 10~15 parts of thixotropic agent, 5~8 parts of polymerization inhibitors, 25~45 parts of diluents and 20~35 parts of accelerating agents, unsaturated polyester resin is mixed with thixotropic agent, and sequentially add filler, epoxy acrylic resin mixture, polyallylamine, hydroxymethyl cellulose, polymerization inhibitor, diluent and accelerating agent, after being stirred, obtain blank, after blank is vacuumized, it is filling, up to weather-proof cloud stone glue.The weather-proof cloud stone glue of gained of the invention has excellent adhesive fastness and weatherability.
Description
Technical field
The invention discloses a kind of preparation methods of weather-proof cloud stone glue, belong to stone material adhesive technical field.
Background technology
In order to pursue the beautiful, safe and healthy of building, energy-saving and environmental protection and natural harmony, architects are more and more
Interior exterior finish ornament materials as building of selection lithotome, artificial board and various composite decorating boards.Due to stone material
A large amount of uses of curtain wall, dry-fasten stone curtain wall construction are used as a kind of advanced mounting process, are applied in building exterior wall face decoration
At most.
Cloud stone glue is to be divided into two kinds of raw materials of epoxy resin and unsaturated-resin by cloud stone glue to make, what unsaturated-resin made
Certain of cloud stone glue can cure in a humid environment, and effect is also fine.In addition, the excellent of cloud stone glue performance is mainly reflected in
Hardness, toughness, rapid curing, polishability, weather-proof, corrosion-resistant etc..
The main component of cloud stone glue is unsaturated polyester resin, peroxide and the other modified materials of addition and appropriate solid
Agent, the effects that capable of playing quickly positioning and repairing and bond, the bonding being suitable between material of the same race can be widely used for building
Stone material, ceramics, vitrified tile splice, bond, and belong to rigid combination.Its advantage is that hardening time is short, is adjusted convenient for construction, but
Since unsaturated polyester resin and curing agent fix the ratio great disparity of formula（Typically 100：3）, the easy imbalance of manual operation, if
The addition of curing agent is more than that 3% colloid may be caused to become fragile, and reduces adhesive property.Cloud stone glue main body in wet environment simultaneously
Resin can be hydrolyzed gradually, and adhesion strength will be caused drastically to decline or even completely lose, therefore be unsuitable for applying in moist place
Work, if air humidity it is excessive also result in colloid surface glue hand, and cloud stone glue influenced by the variation of temperature it is bigger, intolerant to height
Temperature, easy-weathering, should not under the lower weather of temperature constructing operation.Inadequate because shearing, stress is big, makees in the temperature difference and vibrations condition
Displacement with lower generation is bigger, is easy cracking, and particularly for moist and wall of the sunlight without irradiation, service life is shorter.Therefore
Cannot undertake has the function of structural load；In addition there are one deficiencies for cloud stone glue, i.e., without deoiling treatment, are easy to ooze oil
Stone material is penetrated into, stone material is caused to pollute.It is bonded so cloud stone glue is a kind of non-structural carrying such as positioning, repairing suitable for stone material
The stone adhesive of purposes.Cloud stone glue also needs to study it there is also the bad problem of adhesive fastness and weatherability at present.
Invention content
The present invention solves the technical problem of：For the bad problem of traditional marble gluing knot fastness and weatherability,
Provide a kind of preparation method of weather-proof cloud stone glue.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）By epoxy resin and polymerization inhibitor in mass ratio 100：1~100：3 are stirred, and obtain epoxy resin composition, by propylene
Acid and catalyst in mass ratio 50：1~50：3 mixing, obtain acrylic acid mixture, and acrylic acid mixture and epoxy resin are mixed
Object is 0.5 in mass ratio：1~0.7：After the mixing of 1 heating stirring, cooling obtains pretreatment epoxy acrylic resin, adjusts pretreatment
After epoxy acrylic resin pH, continue to cool down, obtains epoxy acrylic resin mixture；
（2）By soluble starch and water in mass ratio 1：10~2：10 mixing, obtain starch mixture, adjust starch mixture pH,
Pretreated starch mixture is obtained, by pretreated starch mixture and potassium permanganate in mass ratio 50：1~50：2 mixing, obtain pre- place
Oxidized starch is managed, by pretreatment oxidized starch cooling, and the glutaraldehyde of 0.02~0.03 times of pretreatment oxidized starch quality is added,
It is stirred, obtains precrosslink oxidized starch, aoxidized by precrosslink oxidized starch isothermal holding, and by the precrosslink after isothermal holding
Starch and diisocyanate in mass ratio 20：3~20：5 mixing, continue insulation reaction, obtain starch adhesive；
（3）It counts in parts by weight, weighs 120~150 parts of unsaturated polyester resins, 80~90 parts of fillers, 50~80 parts of rings successively
Oxypropylene acid resin mixture, 50~70 parts of starch adhesives, 15~20 parts of polyallylamines, 12~18 parts of hydroxymethyl celluloses,
10~15 parts of thixotropic agent, 5~8 parts of polymerization inhibitors, 25~45 parts of diluents and 20~35 parts of accelerating agents, by unsaturated polyester resin with
Thixotropic agent mixes, and sequentially adds filler, epoxy acrylic resin mixture, polyallylamine, hydroxymethyl cellulose, polymerization inhibitor,
Diluent and accelerating agent after being stirred, obtain blank, filling to get weather-proof cloud stone glue after blank is vacuumized.
Step（1）The epoxy resin is any one in E50 types epoxy resin or E51 type epoxy resin.
The polymerization inhibitor is benzoquinones, any one in hydroquinone or tert-butyl catechol.
Step（1）The catalyst is n,N-Dimethylaniline, any one in benzyltrimethylammonium chloride or triethanolamine
Kind.
Step（2）The diisocyanate is toluene di-isocyanate(TDI), isophorone diisocyanate or diphenyl methane
Any one in diisocyanate.
Step（3）The unsaturated polyester resin is m-phthalate unsaturated polyester resin, metaphenylene unsaturated polyester resin
Or any one in Bisphenol a unsaturated polyester resin.
Step（3）The filler is barium sulfate, any one in calcium carbonate or barite.
Step（3）The thixotropic agent is any one in rilanit special or organobentonite.
Step（3）The diluent is vinyltoluene, vinyl diethylene glycol ether, diethylene glycol divinyl ether, neighbour
Two or more arbitrary mixture in dially phthalate.
Step（3）The accelerating agent be cobalt naphthenate, dimethylaniline, any one in diethylaniline or two kinds it is mixed
Close object.
The beneficial effects of the invention are as follows：
（1）Epoxy acrylic resin mixture is added when preparing weather-proof cloud stone glue in the feed by the present invention, first, epoxy third
Containing the active ingredient epoxy acrylic resin that acrylic acid epoxy is modified in olefin(e) acid resin compound, in epoxy acrylic resin
There is epoxy resin, the epoxy group in epoxy resin can cure after use for acrylic acid one end, to keep bonding for product firm
Degree is improved, and due to the solidification of epoxy acrylic, and the water resistance of product effectively improves, secondly, epoxy acrylic
Active ingredient in resin compound has photo-curable, and epoxy acrylic resin can cure under illumination condition, to make production
Product in use can be with the growth of usage time, and the adhesive fastness of product improves, and then improves the weatherability of product；
（2）The present invention uses starch adhesive when preparing weather-proof cloud stone glue, on the one hand, the starch in starch adhesive is passing through
After crossing modification, adhesive fastness and water resistance are improved, to after being added in product, make the adhesive fastness of product
It is further increased with water resistance, and since hydroxyl is contained on modified starch surface, it can be with the hydroxymethyl cellulose surface of addition
Hydroxyl and unsaturated polyester resin in unsaturated bond reaction, to make the crosslinking degree of interiors of products improve, and then make production
The adhesive fastness and weatherability of product improve, and on the other hand, starch adhesive contains diisocyanate, after being added in product, no
Generation carbon dioxide and amine substance, the carbon dioxide of generation can be only decomposed when meeting water can be such that the polyallylamine in product occurs
Crosslinking, makes the adhesive fastness of product improve, the amine substance of generation can promote in epoxy acrylic resin mixture it is effective at
Divide and crosslink, is further increased to make the knot stability of product improve, moreover, diisocyanate can be in use to ring
Active ingredient in oxypropylene acid resin mixture is modified, to improve the photo-curable of epoxy acrylic resin, in turn
The adhesive fastness and weatherability for making product further increase.
Specific implementation mode
By epoxy resin and polymerization inhibitor in mass ratio 100：1~100：3 are mixed in beaker, in temperature be 100~110
DEG C, rotating speed be 200~280r/min under conditions of, be stirred 10~15min, obtain epoxy resin composition, by acrylic acid with
Catalyst in mass ratio 50：1~50：3 mixing are 45~55 DEG C in temperature, under conditions of rotating speed is 200~250r/min, stir
After mixing 15~30min of mixing, acrylic acid mixture is obtained, is 0.5 in mass ratio by acrylic acid mixture and epoxy resin composition：
1~0.7：1 in temperature be 110~120 DEG C, rotating speed be 250~300r/min under conditions of, after being stirred 1~2h, obtain epoxy
Epoxy resin acrylic acid mixture is cooled to 55~65 DEG C, obtains pretreatment epoxy acrylic resin by resin acrylic acid mixture,
After adjusting pretreatment epoxy acrylic resin pH to 12~14 with potassium hydroxide, and continue to be cooled to 40~45 DEG C, obtains epoxy third
Olefin(e) acid resin compound；By soluble starch and water in mass ratio 1：10~2：10 mixing are 45~55 DEG C in temperature, and rotating speed is
Under conditions of 220~300r/min, after being stirred 10~30min, starch mixture is obtained, starch mixture pH is adjusted with hydrochloric acid
To 1.8~2.2, pretreated starch mixture is obtained, by pretreated starch mixture and potassium permanganate in mass ratio 50：1~50：2
Mixing is 55~60 DEG C in temperature, under conditions of rotating speed is 200~220r/min, after being stirred 40~60min, obtains pre- place
Oxidized starch is managed, pretreatment oxidized starch is cooled to 38~42 DEG C, and pretreatment oxidized starch quality 0.02~0.03 is added
Glutaraldehyde again is 38~42 DEG C in temperature, after rotating speed is stirred 3~5h under conditions of being 200~300r/min, must pre-pay
Join oxidized starch, precrosslink oxidized starch is moved into baking oven, under conditions of temperature is 85~90 DEG C, 48~50h of isothermal holding,
And by precrosslink oxidized starch and the diisocyanate in mass ratio 20 after isothermal holding：3~20：5 mixing, in temperature be 40~
50 DEG C, under conditions of rotating speed is 220~300r/min, it is stirred 20~40min, obtains modified starch, by modified starch in temperature
Degree is 8~10h of isothermal holding under conditions of 120~140 DEG C, obtains starch adhesive；It counts in parts by weight, weigh 120 successively~
150 parts of unsaturated polyester resins, 80~90 parts of fillers, 50~80 parts of epoxy acrylic resin mixtures, 50~70 parts of amylans
Glutinous agent, 15~20 parts of polyallylamines, 12~18 parts of hydroxymethyl celluloses, 10~15 parts of thixotropic agent, 5~8 parts of polymerization inhibitors, 25~45
Unsaturated polyester resin and thixotropic agent are mixed in batch mixer by part diluent and 20~35 parts of accelerating agents, and successively to batch mixing
Filler, epoxy acrylic resin mixture, polyallylamine, hydroxymethyl cellulose, polymerization inhibitor, diluent and promotion are added in machine
Agent is 65~75 DEG C in temperature, after rotating speed is stirred 30~80min under conditions of being 250~350r/min, obtains blank, will
It is filling to get weather-proof cloud stone glue after blank vacuumizes 70~75min.The epoxy resin is E50 types epoxy resin or E51
Any one in type epoxy resin.The polymerization inhibitor is benzoquinones, any one in hydroquinone or tert-butyl catechol.It is described
Catalyst is n,N-Dimethylaniline, any one in benzyltrimethylammonium chloride or triethanolamine.The diisocyanate is
Any one in toluene di-isocyanate(TDI), isophorone diisocyanate or methyl diphenylene diisocyanate.The unsaturation
Polyester resin is m-phthalate unsaturated polyester resin, in metaphenylene unsaturated polyester resin or Bisphenol a unsaturated polyester resin
Any one.The filler is barium sulfate, any one in calcium carbonate or barite.The thixotropic agent is rilanit special or has
Any one in machine bentonite.The diluent is vinyltoluene, vinyl diethylene glycol ether, diethylene glycol divinyl base
Two or more arbitrary mixture in ether, diallyl phthalate.The accelerating agent is cobalt naphthenate, dimethyl
Any one in aniline, diethylaniline or two kinds of mixture.
Example 1
By epoxy resin and polymerization inhibitor in mass ratio 100：3 are mixed in beaker, in temperature be 110 DEG C, rotating speed 280r/min
Under conditions of, it is stirred 15min, obtains epoxy resin composition, by acrylic acid and catalyst in mass ratio 50：3 mixing, Yu Wen
Degree is 55 DEG C, under conditions of rotating speed is 250r/min, after being stirred 30min, acrylic acid mixture is obtained, by acrylic acid mixture
It is 0.5 in mass ratio with epoxy resin composition：1 in temperature be 120 DEG C, rotating speed be 300r/min under conditions of, be stirred
After 2h, epoxy resin acrylic acid mixture is obtained, epoxy resin acrylic acid mixture is cooled to 65 DEG C, obtains pretreatment propylene oxide
Acid resin after adjusting pretreatment epoxy acrylic resin pH to 14 with potassium hydroxide, and continues to be cooled to 45 DEG C, obtains propylene oxide
Acid resin mixture；By soluble starch and water in mass ratio 2：10 mixing are 55 DEG C in temperature, and rotating speed is the item of 300r/min
Under part, after being stirred 30min, starch mixture is obtained, starch mixture pH to 2.2 is adjusted with hydrochloric acid, it is mixed to obtain pretreated starch
Object is closed, by pretreated starch mixture and potassium permanganate in mass ratio 50：2 mixing, in temperature be 60 DEG C, rotating speed 220r/min
Under conditions of, after being stirred 60min, pretreatment oxidized starch is obtained, pretreatment oxidized starch is cooled to 42 DEG C, and be added pre-
The glutaraldehyde for handling 0.03 times of oxidized starch quality is 42 DEG C in temperature, and rotating speed is stirred 5h under conditions of being 300r/min
Afterwards, precrosslink oxidized starch is obtained, precrosslink oxidized starch is moved into baking oven, under the conditions of at a temperature of 90 °C, isothermal holding
50h, and by precrosslink oxidized starch and the diisocyanate in mass ratio 20 after isothermal holding：5 mixing, in temperature be 50 DEG C,
Under conditions of rotating speed is 300r/min, it is stirred 40min, obtains modified starch, the condition for being 140 DEG C in temperature by modified starch
Lower isothermal holding 10h, obtains starch adhesive；It counts in parts by weight, weighs 150 parts of unsaturated polyester resins successively, 90 parts of fillers,
80 parts of epoxy acrylic resin mixtures, 70 parts of starch adhesives, 20 parts of polyallylamines, 18 parts of hydroxymethyl celluloses, 15 parts are touched
Become agent, 8 parts of polymerization inhibitors, 45 parts of diluents and 35 parts of accelerating agents, unsaturated polyester resin and thixotropic agent be mixed in batch mixer,
And filler is added into batch mixer successively, epoxy acrylic resin mixture, polyallylamine, hydroxymethyl cellulose, polymerization inhibitor is dilute
Agent and accelerating agent are released, is 75 DEG C in temperature, after rotating speed is stirred 80min under conditions of being 350r/min, blank is obtained, by blank
It is filling to get weather-proof cloud stone glue after vacuumizing 75min.The epoxy resin is E50 type epoxy resin.The polymerization inhibitor is
Benzoquinones.The catalyst is N, accelerine.The diisocyanate is toluene di-isocyanate(TDI).The unsaturated polyester (UP)
Resin is m-phthalate unsaturated polyester resin.The filler is barium sulfate.The thixotropic agent is rilanit special.The diluent
For vinyltoluene.The accelerating agent is cobalt naphthenate.
Example 2
By soluble starch and water in mass ratio 2：10 mixing are 55 DEG C in temperature, under conditions of rotating speed is 300r/min, stir
After mixing 30min, starch mixture is obtained, starch mixture pH to 2.2 is adjusted with hydrochloric acid, obtains pretreated starch mixture, it will be pre-
Handle starch mixture and potassium permanganate in mass ratio 50：2 mixing, in temperature be 60 DEG C, rotating speed be 220r/min under conditions of,
After being stirred 60min, pretreatment oxidized starch is obtained, pretreatment oxidized starch is cooled to 42 DEG C, and pretreatment oxidation is added
The glutaraldehyde that 0.03 times of starch quality is 42 DEG C in temperature, after rotating speed is stirred 5h under conditions of being 300r/min, must pre-pay
Join oxidized starch, precrosslink oxidized starch is moved into baking oven, under the conditions of at a temperature of 90 °C, isothermal holding 50h, and will heat preservation
Treated precrosslink oxidized starch and diisocyanate in mass ratio 20：5 mixing, in temperature be 50 DEG C, rotating speed 300r/
Under conditions of min, it is stirred 40min, obtains modified starch, isothermal holding under conditions of being 140 DEG C in temperature by modified starch
10h obtains starch adhesive；It counts in parts by weight, weighs 150 parts of unsaturated polyester resins, 90 parts of fillers, 80 parts of asphalt mixtures modified by epoxy resin successively
Fat, 70 parts of starch adhesives, 20 parts of polyallylamines, 18 parts of hydroxymethyl celluloses, 15 parts of thixotropic agent, 8 parts of polymerization inhibitors, 45 parts of dilutions
Unsaturated polyester resin and thixotropic agent are mixed in batch mixer, and are added fill out into batch mixer successively by agent and 35 parts of accelerating agents
Material, epoxy resin, polyallylamine, hydroxymethyl cellulose, polymerization inhibitor, diluent and accelerating agent are 75 DEG C in temperature, and rotating speed is
After being stirred 80min under conditions of 350r/min, blank is obtained, it is filling to get weather-proof cloud after blank is vacuumized 75min
Stone glue.The epoxy resin is E50 type epoxy resin.The polymerization inhibitor is benzoquinones.The catalyst is N, accelerine.
The diisocyanate is toluene di-isocyanate(TDI).The unsaturated polyester resin is m-phthalate unsaturated polyester resin.It is described
Filler is barium sulfate.The thixotropic agent is rilanit special.The diluent is vinyltoluene.The accelerating agent is aphthenic acids
Cobalt.
Example 3
By epoxy resin and polymerization inhibitor in mass ratio 100：3 are mixed in beaker, in temperature be 110 DEG C, rotating speed 280r/min
Under conditions of, it is stirred 15min, obtains epoxy resin composition, by acrylic acid and catalyst in mass ratio 50：3 mixing, Yu Wen
Degree is 55 DEG C, under conditions of rotating speed is 250r/min, after being stirred 30min, acrylic acid mixture is obtained, by acrylic acid mixture
It is 0.5 in mass ratio with epoxy resin composition：1 in temperature be 120 DEG C, rotating speed be 300r/min under conditions of, be stirred
After 2h, epoxy resin acrylic acid mixture is obtained, epoxy resin acrylic acid mixture is cooled to 65 DEG C, obtains pretreatment propylene oxide
Acid resin after adjusting pretreatment epoxy acrylic resin pH to 14 with potassium hydroxide, and continues to be cooled to 45 DEG C, obtains propylene oxide
Acid resin mixture；By soluble starch and water in mass ratio 2：10 mixing are 55 DEG C in temperature, and rotating speed is the item of 300r/min
Under part, after being stirred 30min, starch mixture is obtained, starch mixture pH to 2.2 is adjusted with hydrochloric acid, it is mixed to obtain pretreated starch
Object is closed, by pretreated starch mixture and potassium permanganate in mass ratio 50：2 mixing, in temperature be 60 DEG C, rotating speed 220r/min
Under conditions of, after being stirred 60min, pretreatment oxidized starch is obtained, pretreatment oxidized starch is cooled to 42 DEG C, and be added pre-
The glutaraldehyde for handling 0.03 times of oxidized starch quality is 42 DEG C in temperature, and rotating speed is stirred 5h under conditions of being 300r/min
Afterwards, precrosslink oxidized starch is obtained, precrosslink oxidized starch is moved into baking oven, under the conditions of at a temperature of 90 °C, isothermal holding
50h obtains starch adhesive；It counts in parts by weight, weighs 150 parts of unsaturated polyester resins, 90 parts of fillers, 80 parts of epoxies third successively
Olefin(e) acid resin compound, 70 parts of starch adhesives, 20 parts of polyallylamines, 18 parts of hydroxymethyl celluloses, 15 parts of thixotropic agent, 8 parts of resistances
Unsaturated polyester resin and thixotropic agent are mixed in batch mixer by poly- agent, 45 parts of diluents and 35 parts of accelerating agents, and successively to mixed
Filler, epoxy acrylic resin mixture, polyallylamine, hydroxymethyl cellulose, polymerization inhibitor, diluent and promotion are added in material machine
Agent is 75 DEG C in temperature, after rotating speed is stirred 80min under conditions of being 350r/min, obtains blank, blank is vacuumized
It is filling to get weather-proof cloud stone glue after 75min.The epoxy resin is E50 type epoxy resin.The polymerization inhibitor is benzoquinones.Institute
It is N, accelerine to state catalyst.The diisocyanate is toluene di-isocyanate(TDI).The unsaturated polyester resin is
M-phthalate unsaturated polyester resin.The filler is barium sulfate.The thixotropic agent is rilanit special.The diluent is ethylene
Base toluene.The accelerating agent is cobalt naphthenate.
Example 4
By epoxy resin and polymerization inhibitor in mass ratio 100：3 are mixed in beaker, in temperature be 110 DEG C, rotating speed 280r/min
Under conditions of, it is stirred 15min, obtains epoxy resin composition, by acrylic acid and catalyst in mass ratio 50：3 mixing, Yu Wen
Degree is 55 DEG C, under conditions of rotating speed is 250r/min, after being stirred 30min, acrylic acid mixture is obtained, by acrylic acid mixture
It is 0.5 in mass ratio with epoxy resin composition：1 in temperature be 120 DEG C, rotating speed be 300r/min under conditions of, be stirred
After 2h, epoxy resin acrylic acid mixture is obtained, epoxy resin acrylic acid mixture is cooled to 65 DEG C, obtains pretreatment propylene oxide
Acid resin after adjusting pretreatment epoxy acrylic resin pH to 14 with potassium hydroxide, and continues to be cooled to 45 DEG C, obtains propylene oxide
Acid resin mixture；By soluble starch and water in mass ratio 2：10 mixing are 55 DEG C in temperature, and rotating speed is the item of 300r/min
Under part, after being stirred 30min, starch mixture is obtained, starch mixture pH to 2.2 is adjusted with hydrochloric acid, it is mixed to obtain pretreated starch
Object is closed, by pretreated starch mixture and potassium permanganate in mass ratio 50：2 mixing, in temperature be 60 DEG C, rotating speed 220r/min
Under conditions of, after being stirred 60min, pretreatment oxidized starch is obtained, pretreatment oxidized starch is cooled to 42 DEG C, and be added pre-
The glutaraldehyde for handling 0.03 times of oxidized starch quality is 42 DEG C in temperature, and rotating speed is stirred 5h under conditions of being 300r/min
Afterwards, precrosslink oxidized starch is obtained, precrosslink oxidized starch is moved into baking oven, under the conditions of at a temperature of 90 °C, isothermal holding
50h, and by precrosslink oxidized starch and the diisocyanate in mass ratio 20 after isothermal holding：5 mixing, in temperature be 50 DEG C,
Under conditions of rotating speed is 300r/min, it is stirred 40min, obtains modified starch, the condition for being 140 DEG C in temperature by modified starch
Lower isothermal holding 10h, obtains starch adhesive；It counts in parts by weight, weighs 150 parts of unsaturated polyester resins successively, 90 parts of fillers,
80 parts of epoxy acrylic resin mixtures, 70 parts of starch adhesives, 18 parts of hydroxymethyl celluloses, 15 parts of thixotropic agent, 8 parts of inhibitions
Unsaturated polyester resin and thixotropic agent are mixed in batch mixer by agent, 45 parts of diluents and 35 parts of accelerating agents, and successively to batch mixing
Filler, epoxy acrylic resin mixture, hydroxymethyl cellulose, polymerization inhibitor, diluent and accelerating agent are added in machine, is in temperature
75 DEG C, after rotating speed is stirred 80min under conditions of being 350r/min, blank is obtained, it is filling after blank is vacuumized 75min, i.e.,
Obtain weather-proof cloud stone glue.The epoxy resin is E50 type epoxy resin.The polymerization inhibitor is benzoquinones.The catalyst is N, N-
Dimethylaniline.The diisocyanate is toluene di-isocyanate(TDI).The unsaturated polyester resin is that adjacent benzene-type unsaturation is poly-
Ester resin.The filler is barium sulfate.The thixotropic agent is rilanit special.The diluent is vinyltoluene.The rush
It is cobalt naphthenate into agent.
Example 5
By epoxy resin and polymerization inhibitor in mass ratio 100：3 are mixed in beaker, in temperature be 110 DEG C, rotating speed 280r/min
Under conditions of, it is stirred 15min, obtains epoxy resin composition, by acrylic acid and catalyst in mass ratio 50：3 mixing, Yu Wen
Degree is 55 DEG C, under conditions of rotating speed is 250r/min, after being stirred 30min, acrylic acid mixture is obtained, by acrylic acid mixture
It is 0.5 in mass ratio with epoxy resin composition：1 in temperature be 120 DEG C, rotating speed be 300r/min under conditions of, be stirred
After 2h, epoxy resin acrylic acid mixture is obtained, epoxy resin acrylic acid mixture is cooled to 65 DEG C, obtains pretreatment propylene oxide
Acid resin after adjusting pretreatment epoxy acrylic resin pH to 14 with potassium hydroxide, and continues to be cooled to 45 DEG C, obtains propylene oxide
Acid resin mixture；By soluble starch and water in mass ratio 2：10 mixing are 55 DEG C in temperature, and rotating speed is the item of 300r/min
Under part, after being stirred 30min, starch mixture is obtained, starch mixture pH to 2.2 is adjusted with hydrochloric acid, it is mixed to obtain pretreated starch
Object is closed, by pretreated starch mixture and potassium permanganate in mass ratio 50：2 mixing, in temperature be 60 DEG C, rotating speed 220r/min
Under conditions of, after being stirred 60min, pretreatment oxidized starch is obtained, pretreatment oxidized starch is cooled to 42 DEG C, and be added pre-
The glutaraldehyde for handling 0.03 times of oxidized starch quality is 42 DEG C in temperature, and rotating speed is stirred 5h under conditions of being 300r/min
Afterwards, precrosslink oxidized starch is obtained, precrosslink oxidized starch is moved into baking oven, under the conditions of at a temperature of 90 °C, isothermal holding
50h, and by precrosslink oxidized starch and the diisocyanate in mass ratio 20 after isothermal holding：5 mixing, in temperature be 50 DEG C,
Under conditions of rotating speed is 300r/min, it is stirred 40min, obtains modified starch, the condition for being 140 DEG C in temperature by modified starch
Lower isothermal holding 10h, obtains starch adhesive；It counts in parts by weight, weighs 150 parts of unsaturated polyester resins successively, 90 parts of fillers,
80 parts of epoxy acrylic resin mixtures, 70 parts of starch adhesives, 20 parts of polyallylamines, 15 parts of thixotropic agent, 8 parts of polymerization inhibitors, 45
Unsaturated polyester resin and thixotropic agent are mixed in batch mixer by part diluent and 35 parts of accelerating agents, and successively into batch mixer
Filler, epoxy acrylic resin mixture, polyallylamine, polymerization inhibitor, diluent and accelerating agent is added, is 75 DEG C in temperature, turns
After speed is stirred 80min under conditions of being 350r/min, blank is obtained, it is filling to get weather-proof after blank is vacuumized 75min
Type cloud stone glue.The epoxy resin is E50 type epoxy resin.The polymerization inhibitor is benzoquinones.The catalyst is N, N- dimethyl
Aniline.The diisocyanate is toluene di-isocyanate(TDI).The unsaturated polyester resin is m-phthalate unsaturated polyester resin.
The filler is barium sulfate.The thixotropic agent is rilanit special.The diluent is vinyltoluene.The accelerating agent is ring
Alkanoic acid cobalt.
Comparative example：The cloud stone glue of Anhui building materials Co., Ltd production.
1 to 5 gained cloud stone glue of example and comparative example product are subjected to performance detection, specific detection method is as follows：
According to its performance of JC/T989 standard detections, specific testing result is as shown in table 1：
Table 1：Performance detection table
By 1 testing result of table it is found that the weather-proof cloud stone glue of present invention gained has excellent adhesive fastness and weatherability.
Claims (10)
1. a kind of preparation method of weather-proof cloud stone glue, which is characterized in that specifically preparation method is：
（1）By epoxy resin and polymerization inhibitor in mass ratio 100：1~100：3 are stirred, and obtain epoxy resin composition, by propylene
Acid and catalyst in mass ratio 50：1~50：3 mixing, obtain acrylic acid mixture, and acrylic acid mixture and epoxy resin are mixed
Object is 0.5 in mass ratio：1~0.7：After the mixing of 1 heating stirring, cooling obtains pretreatment epoxy acrylic resin, adjusts pretreatment
After epoxy acrylic resin pH, continue to cool down, obtains epoxy acrylic resin mixture；
（2）By soluble starch and water in mass ratio 1：10~2：10 mixing, obtain starch mixture, adjust starch mixture pH,
Pretreated starch mixture is obtained, by pretreated starch mixture and potassium permanganate in mass ratio 50：1~50：2 mixing, obtain pre- place
Oxidized starch is managed, by pretreatment oxidized starch cooling, and the glutaraldehyde of 0.02~0.03 times of pretreatment oxidized starch quality is added,
It is stirred, obtains precrosslink oxidized starch, aoxidized by precrosslink oxidized starch isothermal holding, and by the precrosslink after isothermal holding
Starch and diisocyanate in mass ratio 20：3~20：5 mixing, continue insulation reaction, obtain starch adhesive；
（3）It counts in parts by weight, weighs 120~150 parts of unsaturated polyester resins, 80~90 parts of fillers, 50~80 parts of rings successively
Oxypropylene acid resin mixture, 50~70 parts of starch adhesives, 15~20 parts of polyallylamines, 12~18 parts of hydroxymethyl celluloses,
10~15 parts of thixotropic agent, 5~8 parts of polymerization inhibitors, 25~45 parts of diluents and 20~35 parts of accelerating agents, by unsaturated polyester resin with
Thixotropic agent mixes, and sequentially adds filler, epoxy acrylic resin mixture, polyallylamine, hydroxymethyl cellulose, polymerization inhibitor,
Diluent and accelerating agent after being stirred, obtain blank, filling to get weather-proof cloud stone glue after blank is vacuumized.
2. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：Step（1）The ring
Oxygen resin is any one in E50 types epoxy resin or E51 type epoxy resin.
3. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：The polymerization inhibitor is benzene
Any one in quinone, hydroquinone or tert-butyl catechol.
4. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：Step（1）It is described to urge
Agent is n,N-Dimethylaniline, any one in benzyltrimethylammonium chloride or triethanolamine.
5. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：Step（2）Described two
Isocyanates is toluene di-isocyanate(TDI), any one in isophorone diisocyanate or methyl diphenylene diisocyanate.
6. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：Step（3）It is described not
Saturated polyester resin is m-phthalate unsaturated polyester resin, metaphenylene unsaturated polyester resin or bisphenol A-type unsaturated polyester (UP) tree
Any one in fat.
7. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：Step（3）It is described to fill out
Expect to be barium sulfate, any one in calcium carbonate or barite.
8. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：Step（3）It is described to touch
Any one in becoming agent as rilanit special or organobentonite.
9. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：Step（3）It is described dilute
It is to appoint in vinyltoluene, vinyl diethylene glycol ether, diethylene glycol divinyl ether, diallyl phthalate to release agent
It anticipates two or more mixture.
10. a kind of preparation method of weather-proof cloud stone glue according to claim 1, it is characterised in that：Step（3）The rush
Into the mixture that agent is any one in cobalt naphthenate, dimethylaniline, diethylaniline or two kinds.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810137275.8A CN108329881A (en) | 2018-02-10 | 2018-02-10 | A kind of preparation method of weather-proof cloud stone glue |
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| CN201810137275.8A CN108329881A (en) | 2018-02-10 | 2018-02-10 | A kind of preparation method of weather-proof cloud stone glue |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057505A (en) * | 2019-12-25 | 2020-04-24 | 常州华日升反光材料有限公司 | Special pressure-sensitive adhesive for cement surface prism film and preparation method thereof |
| CN116676058A (en) * | 2023-07-03 | 2023-09-01 | 广东晋泽科技有限公司 | High-strength high-toughness starch adhesive and preparation process thereof |
| CN117089309A (en) * | 2023-08-28 | 2023-11-21 | 江苏大力士投资有限公司 | Functional marble adhesive and preparation method thereof |
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2018
- 2018-02-10 CN CN201810137275.8A patent/CN108329881A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057505A (en) * | 2019-12-25 | 2020-04-24 | 常州华日升反光材料有限公司 | Special pressure-sensitive adhesive for cement surface prism film and preparation method thereof |
| CN111057505B (en) * | 2019-12-25 | 2021-12-24 | 常州华日升反光材料有限公司 | Special pressure-sensitive adhesive for cement surface prism film and preparation method thereof |
| CN116676058A (en) * | 2023-07-03 | 2023-09-01 | 广东晋泽科技有限公司 | High-strength high-toughness starch adhesive and preparation process thereof |
| CN116676058B (en) * | 2023-07-03 | 2023-12-22 | 广东晋泽科技有限公司 | High-strength high-toughness starch adhesive and preparation process thereof |
| CN117089309A (en) * | 2023-08-28 | 2023-11-21 | 江苏大力士投资有限公司 | Functional marble adhesive and preparation method thereof |
| CN117089309B (en) * | 2023-08-28 | 2024-04-23 | 江苏大力士投资有限公司 | Functional marble adhesive and preparation method thereof |
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Application publication date: 20180727 |