CN108047433A - A kind of unsaturated-resin and preparation method for artificial stone and its application in stock white and artificial stone - Google Patents
A kind of unsaturated-resin and preparation method for artificial stone and its application in stock white and artificial stone Download PDFInfo
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- CN108047433A CN108047433A CN201810022366.7A CN201810022366A CN108047433A CN 108047433 A CN108047433 A CN 108047433A CN 201810022366 A CN201810022366 A CN 201810022366A CN 108047433 A CN108047433 A CN 108047433A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
- C09D17/008—Titanium dioxide
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The invention discloses a kind of unsaturated-resins for artificial stone, and preparing the raw material of modified unsaturated resin includes：Cis-1, tetrahydrophthalic anhydride as acid starting material；Propylene glycol, diethylene glycol and neopentyl glycol as raw polyol；Wherein acid-alcohol ratio is 1:Mole total amount of (1 1.1), propylene glycol and diethylene glycol and the molar ratio of neopentyl glycol are (0.80 0.95):0.1；Further include styrene and polymerization inhibitor, the styrene dosage is 30% the 33% of acid starting material and raw polyol gross mass, and the polymerization inhibitor is acid starting material and raw polyol gross mass 0.01 0.05%.Preparation method and its application in stock white and artificial stone the invention also discloses unsaturated-resin.The present invention unsaturated-resin can with titanium dioxide high polymeric, for improving the glossiness of artificial stone or daylighting tile and mechanical performance.
Description
Technical field
The present invention relates to technical field of polymer materials, are set more specifically to a kind of for the unsaturated of artificial stone
Fat and preparation method thereof and artificial stone stock white.
Background technology
Resin based artificial stone is developed in recent years using resin as matrix, is added in according still further to certain proportion different thin
The filler material of degree, the mill base of different colours are mixed with raw materials such as auxiliary agents, by stirring, casting, being gelled, the series of process such as curing
A kind of new decorative material for building made of process.Engineered stone products currently on the market, have magnificent stone, clean beautiful stone, can beautiful stone
Etc., it can be collectively referred to as " artificial stone ".The radioactive element content of natural marble is often exceeded, can do harm to huamn body；And
Resin based artificial stone also has the texture, granitic hard of natural marble except the problem of radioactive element is exceeded is not present,
And with not fugitive color, easy cleaning maintenance, water-fast, heat-resisting, grease proofing, anti-corrosion, it is moisture-proof, mothproof, prevent fires many advantages, such as；And
And artificial stone can indiscriminately ad. as one wishes be fabricated to various shapes in different poses and with different expressions, can reach seamless spliced effect, can make
Go out arbitrary rich and varied color.Therefore artificial stone is widely used in Civil Aviation Airport, bank, hotel, company, writes
In the parlor in many places such as building, meeting room, office, lobby and toilet；It is also widely used in house decoration, such as artificial stone
Table top, kitchen cabinet, sink, sanitary ware etc..
Resin mill base is the raw material of artificial stone (hilllock stone, quartz) and daylighting tile.The primary raw material of stock white be resin with
Titanium dioxide, resin is the unsaturated polyester (UP) tree for saturated polyester resin or low molecular weight used by traditional white slurry
Fat, the not high stock white not polymerizeing either of the degree of polymerization is in manufacture artificial stone or daylighting between this resin and titanium dioxide
There is the problems such as curing not exclusively, hardness declines in watt-hour, slackened the performance of product.In order to avoid in stock white resin to artificial
The influence of stone or daylighting tile performance, industry widespread practice is that the additive amount of mill base is controlled to be no more than 12%, and works as additive amount
During higher than 12%, the mechanical performance of product can be influenced；But when the additive amount of stock white is too low, artificial stone or daylighting tile produce
Application requirement is not achieved in the glossiness of product, therefore limits the scope of application of stock white.
The content of the invention
For the drawbacks described above of the prior art, it is an object of the invention to provide a kind of unsaturated trees for artificial stone
Fat, by being modified to resin, obtain it is a kind of can with the unsaturated-resin of titanium dioxide high polymeric, for improve artificial stone or
The glossiness and mechanical performance of daylighting tile.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of unsaturated-resin for artificial stone, preparing the raw material of modified unsaturated resin includes：
Cis-1, tetrahydrophthalic anhydride as acid starting material；
Propylene glycol, diethylene glycol and neopentyl glycol as raw polyol；
Wherein acid-alcohol ratio is 1:Mole total amount of (1-1.1), propylene glycol and diethylene glycol and the molar ratio of neopentyl glycol are
(0.80-0.95):0.1；
Further including styrene and polymerization inhibitor, the styrene dosage is acid starting material and the 30%-33% of raw polyol gross mass,
The polymerization inhibitor is acid starting material and raw polyol gross mass 0.01-0.05%.
As further embodiment, the molar ratio of cis-1 of the present invention and tetrahydrophthalic anhydride is 1:1, institute
The molar ratio for stating propylene glycol and diethylene glycol is 1:1.
Another object of the present invention is to provide a kind of preparation method of the unsaturated-resin for artificial stone.
A kind of preparation method of unsaturated-resin for artificial stone, including
Step of esterification：Nitrogen will be passed through in reaction kettle, adds cis-1 and tetrahydrophthalic anhydride according to proportioning
Enter into reaction kettle, be added to after then mixing propylene glycol, diethylene glycol and neopentyl glycol by pipeline in reaction kettle, to anti-
Kettle is answered to be heated, the agitating paddle that reaction kettle is started during reactor temperature is raised is stirred material reaction,
Heating temperature is controlled simultaneously, when the temperature of charge in reaction kettle reaches 160 DEG C, when insulation reaction 1-2 is small, then proceedes to heat up
To 210 DEG C, stop heating after the completion of reaction, obtain carboxylate；
Modified-reaction step：Styrene is added to by pipeline in the thinning vessel after having used nitrogen or vacuumize process,
Add in polymerization inhibitor；When above-mentioned carboxylate is cooled to 140-150 DEG C, the carboxylate of reaction kettle is added slowly to thinning with negative pressure
In kettle, the temperature of thinning vessel is controlled below 85 DEG C, and material to the material stirred in thinning vessel is cooled to less than 48 DEG C, obtains half
Finished product；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
As further embodiment, in step of esterification of the present invention, using 220-240 DEG C of conduction oil to anti-
Kettle is answered to be heated.
As further embodiment, preparation method of the present invention is additionally included in carboxylate and is transferred to before thinning vessel to ester
The step of viscosity and acid value of compound are detected, the detection of viscosimeter acidity reach predetermined value, stop heating.
A kind of artificial stone stock white, including titanium dioxide and unsaturated-resin of the present invention, wherein titanium dioxide and insatiable hunger
Mass percent with resin is respectively 20-50% and 50-80%.
As further embodiment, the mass ratio of titanium dioxide and unsaturated-resin of the present invention is 1：3.
A kind of artificial stone, including the following components being calculated in mass percent：
Resin：8-15%,
Filler：70-80%,
Curing agent：0.5-1.5%,
Accelerating agent：0.05-0.1%,
Stock white of the present invention：10-18%.
As further embodiment, resin of the present invention is UPR resins or unsaturated-resin of the present invention.
As further embodiment, filler of the present invention is CaCO3、MgO、Al(OH)3In one kind or amount in more than
Mixing.
Compared with prior art, the invention has the advantages that：
1. the unsaturated-resin of the present invention for artificial stone is applied to artificial stone mill base, with the tree in artificial stone
Fat, filler etc. are fully cured, and improve the glossiness and mechanical strength of artificial stone, meet the needs of application；
2. artificial stone stock white of the present invention is as a result of the modified unsaturated-resin of the present invention, unsaturated-resin
The degree of polymerization between titanium dioxide increases, therefore waits the usage amount that need not strictly control stock white when in use, is more than or low
In the performance that 12% does not interfere with artificial stone or daylighting tile；
3. artificial stone of the present invention has good glossiness and intensity, its application range is expanded.
Specific embodiment
In the following, with reference to specific embodiment, the present invention is described further：
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is the normal of this field unless otherwise instructed
Rule method.
A kind of unsaturated-resin for artificial stone, preparing the raw material of modified unsaturated resin includes：
Cis-1, tetrahydrophthalic anhydride as acid starting material；
Propylene glycol, diethylene glycol and neopentyl glycol as raw polyol；
Wherein acid-alcohol ratio is 1:Mole total amount of (1-1.1), propylene glycol and diethylene glycol and the molar ratio of neopentyl glycol are
(0.80-0.95):0.1；
Further including styrene and polymerization inhibitor, the styrene dosage is acid starting material and the 30%-33% of raw polyol gross mass,
The polymerization inhibitor is acid starting material and raw polyol gross mass 0.01-0.05%.
Tetrahydrophthalic anhydride mainly improves the air-drying property of resin in the present invention, and the solidfied material after curing has preferable insulation
Property, high pressure resistant, corrosion-resistant, shock resistance, cracking resistance become, the advantages that contraction distortion is small.In the present invention, neopentyl glycol is as raw polyol
Synthesize unsaturated-resin, neopentyl glycol, which can substitute part ethylene glycol, has improved the thermolytic mechanism of unsaturated-resin and water-fast
Numerical solution.
As further embodiment, the molar ratio of cis-1 of the present invention and tetrahydrophthalic anhydride is 1:1, institute
The molar ratio for stating propylene glycol and diethylene glycol is 1:1.
Another object of the present invention is to provide a kind of preparation method of the unsaturated-resin for artificial stone.
A kind of preparation method of unsaturated-resin for artificial stone, including
Step of esterification：Nitrogen will be passed through in reaction kettle, adds cis-1 and tetrahydrophthalic anhydride according to proportioning
Enter into reaction kettle, be added to after then mixing propylene glycol, diethylene glycol and neopentyl glycol by pipeline in reaction kettle, to anti-
Kettle is answered to be heated, the agitating paddle that reaction kettle is started during reactor temperature is raised is stirred material reaction,
Heating temperature is controlled simultaneously, when the temperature of charge in reaction kettle reaches 160 DEG C, when insulation reaction 1-2 is small, then proceedes to heat up
To 210 DEG C, stop heating after the completion of reaction, obtain carboxylate；
Modified-reaction step：Styrene is added to by pipeline in the thinning vessel after having used nitrogen or vacuumize process,
Add in polymerization inhibitor；When above-mentioned carboxylate is cooled to 140-150 DEG C, the carboxylate of reaction kettle is added slowly to thinning with negative pressure
In kettle, the temperature of thinning vessel is controlled below 85 DEG C, and material to the material stirred in thinning vessel is cooled to less than 48 DEG C, obtains half
Finished product；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
As further embodiment, in step of esterification of the present invention, using 220-240 DEG C of conduction oil to anti-
Kettle is answered to be heated.
As further embodiment, preparation method of the present invention is additionally included in carboxylate and is transferred to before thinning vessel to ester
The step of viscosity and acid value of compound are detected, the detection of viscosimeter acidity reach predetermined value, stop heating.
A kind of artificial stone stock white, including titanium dioxide and unsaturated-resin of the present invention, wherein titanium dioxide and insatiable hunger
Mass percent with resin is respectively 20-50% and 50-80%.
As further embodiment, the mass ratio of titanium dioxide and unsaturated-resin of the present invention is 1：3.
A kind of artificial stone, including the following components being calculated in mass percent：
Resin：8-15%,
Filler：70-80%,
Curing agent：0.5-1.5%,
Accelerating agent：0.05-0.1%,
Stock white of the present invention：10-18%.
As further embodiment, resin of the present invention is UPR resins or unsaturated-resin of the present invention.
As further embodiment, filler of the present invention is CaCO3、MgO、Al(OH)3In one kind or amount in more than
Mixing.The curing agent is TBPO (the peroxidating 2 ethyl hexanoic acid tert-butyl ester), BPO (benzoyl peroxide), MEKP (peroxidating first
Ethyl ketone), one or both of TBPB (tertiary butyl perbenzoate) mixing.It is described
Embodiment 1
A kind of modified unsaturated polyester resin, preparing the raw material of modified unsaturated polyester resin includes cis-1
Acid anhydride, tetrahydrophthalic anhydride, propylene glycol, diethylene glycol, neopentyl glycol, styrene, polymerization inhibitor；
Wherein acid-alcohol ratio is 1：1, the molar ratio of mole total amount and trihydroxy methyl of propylene glycol and diethylene glycol is 0.80：
0.1；The styrene dosage is the 30% of acid starting material and raw polyol gross mass, and the polymerization inhibitor is 0.01%；
Specific preparation method is as follows：
Step of esterification：Nitrogen will be passed through in reaction kettle, adds cis-1 and tetrahydrophthalic anhydride according to proportioning
Enter into reaction kettle, be added to after then mixing propylene glycol, diethylene glycol and neopentyl glycol by pipeline in reaction kettle, used
200 DEG C of conduction oil heats reaction kettle, and the agitating paddle pair of reaction kettle is started during reactor temperature is raised
Material is stirred reaction, while controls heating temperature, and when the temperature of charge in reaction kettle reaches 160 DEG C, insulation reaction 1 is small
When, then proceed to heat up, up to 210 DEG C, detect acid value and viscosity it is up to standard after, stop heating, obtain carboxylate；
Modified-reaction step：Styrene is added to by pipeline in the thinning vessel after having used nitrogen or vacuumize process,
Add in polymerization inhibitor；When above-mentioned carboxylate is cooled to 140 DEG C, the carboxylate of reaction kettle is added slowly to thinning vessel with negative pressure
In, control the temperature of thinning vessel below 85 DEG C, stir thinning vessel in material to material be cooled to less than 48 DEG C, obtain partly into
Product；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
Embodiment 2
A kind of modified unsaturated polyester resin, preparing the raw material of modified unsaturated polyester resin includes cis-1
Acid anhydride, tetrahydrophthalic anhydride, propylene glycol, diethylene glycol, neopentyl glycol, styrene, polymerization inhibitor；
Wherein acid-alcohol ratio is 1：1.06, the molar ratio of mole total amount and trihydroxy methyl of propylene glycol and diethylene glycol is 0.9：
0.1；The styrene dosage is the 32% of acid starting material and raw polyol gross mass, and the polymerization inhibitor is 0.03%；
Specific preparation method is as follows：
Step of esterification：Nitrogen will be passed through in reaction kettle, adds cis-1 and tetrahydrophthalic anhydride according to proportioning
Enter into reaction kettle, be added to after then mixing propylene glycol, diethylene glycol and neopentyl glycol by pipeline in reaction kettle, used
220 DEG C of conduction oil heats reaction kettle, and the agitating paddle pair of reaction kettle is started during reactor temperature is raised
Material is stirred reaction, while controls heating temperature, and when the temperature of charge in reaction kettle reaches 160 DEG C, insulation reaction 2 is small
When, then proceed to heat up, up to 210 DEG C, detect acid value and viscosity it is up to standard after, stop heating, obtain carboxylate；
Modified-reaction step：Styrene is added to by pipeline in the thinning vessel after having used nitrogen or vacuumize process,
Add in polymerization inhibitor；When above-mentioned carboxylate is cooled to 145 DEG C, the carboxylate of reaction kettle is added slowly to thinning vessel with negative pressure
In, control the temperature of thinning vessel below 85 DEG C, stir thinning vessel in material to material be cooled to less than 48 DEG C, obtain partly into
Product；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
Embodiment 3
A kind of modified unsaturated polyester resin, preparing the raw material of modified unsaturated polyester resin includes cis-1
Acid anhydride, tetrahydrophthalic anhydride, propylene glycol, diethylene glycol, neopentyl glycol, styrene, polymerization inhibitor；
Wherein acid-alcohol ratio is 1：1.1, the molar ratio of mole total amount and trihydroxy methyl of propylene glycol and diethylene glycol is 0.95：
0.1；The styrene dosage is the 33% of acid starting material and raw polyol gross mass, and the polymerization inhibitor is 0.05%；
Specific preparation method is as follows：
Step of esterification：Nitrogen will be passed through in reaction kettle, adds cis-1 and tetrahydrophthalic anhydride according to proportioning
Enter into reaction kettle, be added to after then mixing propylene glycol, diethylene glycol and neopentyl glycol by pipeline in reaction kettle, to anti-
Kettle is answered to carry out heating to heat reaction kettle using 220 DEG C of conduction oil, is started during reactor temperature is raised
The agitating paddle of reaction kettle is stirred material reaction, while controls heating temperature, when the temperature of charge in reaction kettle reaches 160
DEG C when, when insulation reaction 1 is small, then proceed to heat up, up to 210 DEG C, detect acid value and viscosity it is up to standard after, stop heating, obtain
To carboxylate；
Modified-reaction step：Styrene and α-methylstyrene are added to by pipeline has used nitrogen or vacuumize process
In thinning vessel afterwards, polymerization inhibitor is added in；When above-mentioned carboxylate is cooled to 150 DEG C, with negative pressure by the carboxylate of reaction kettle slowly
It is added in thinning vessel, controls the temperature of thinning vessel below 85 DEG C, material to the material stirred in thinning vessel is cooled to 48 DEG C
Hereinafter, semi-finished product are obtained；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
Embodiment 4
A kind of artificial stone stock white, including the unsaturated-resin described in titanium dioxide and embodiment 1, wherein titanium dioxide and insatiable hunger
Mass percent with resin is respectively 20% and 80%.
Embodiment 5
A kind of artificial stone stock white, including the unsaturated-resin described in titanium dioxide and embodiment 2, wherein titanium dioxide and insatiable hunger
Mass percent with resin is respectively 25% and 75%.
Embodiment 6
A kind of artificial stone stock white, including the unsaturated-resin described in titanium dioxide and embodiment 3, wherein titanium dioxide and insatiable hunger
Mass percent with resin is respectively 30% and 70%.
Embodiment 7
A kind of artificial stone, including the following components being calculated in mass percent：
UPR resins：8%th,
Filler：80%th,
Curing agent：1.4%th,
Accelerating agent：0.1%th,
The stock white of embodiment 1：10.5%；
The filler is CaCO3、MgO、Al(OH)3It is 1 according to mass ratio:1:1 ratio mixing；
Preparation method is as follows：UPR resins are added in agitator tank, accelerating agent is added in, is stirring evenly and then adding into stock white,
It stirs evenly, then adds in filler CaCO3、MgO、Al(OH)3And curing agent, it is stirred under vacuum 20 minutes, the slurry being stirred pours into
In mold at a temperature of 60 DEG C curing molding, placed after the demoulding, spontaneous curing to hardness 100%,.
Embodiment 8
A kind of artificial stone, including the following components being calculated in mass percent：
The unsaturated-resin of embodiment 2：15%th,
Filler：70%th,
Curing agent：0.5%th,
Accelerating agent：0.1%th,
The stock white of embodiment 1：14.6%；
The filler is CaCO3、MgO、Al(OH)3It is 1 according to mass ratio:1:1 ratio mixing；
Preparation method is as follows：UPR resins are added in agitator tank, accelerating agent is added in, is stirring evenly and then adding into stock white,
It stirs evenly, then adds in filler CaCO3、MgO、Al(OH)3And curing agent, it is stirred under vacuum 20 minutes, the slurry being stirred pours into
In mold at a temperature of 60 DEG C curing molding, placed after the demoulding, spontaneous curing to hardness 100%,.
Embodiment 9
A kind of artificial stone, including the following components being calculated in mass percent：
UPR resins：10%th,
Filler：72%th,
Curing agent：0.5%th,
Accelerating agent：0.1%th,
The stock white of embodiment 1：17.4%；
The filler is CaCO3、Al(OH)3It is 1 according to mass ratio:1 ratio mixing；
Preparation method is as follows：UPR resins are added in agitator tank, accelerating agent is added in, is stirring evenly and then adding into stock white,
It stirs evenly, then adds in filler CaCO3、Al(OH)3And curing agent, it is stirred under vacuum 20 minutes, the slurry being stirred pours into mold
In at a temperature of 60 DEG C curing molding, placed after the demoulding, spontaneous curing to hardness 100%,.
Comparative example 1
According to the preparation method of above-described embodiment 9, the stock white of embodiment 1 therein is substituted for traditional stock white
(purchased in market) as a comparison case；The dosage of component is as follows in comparative example：
UPR resins：12%th,
Filler：79%th,
Curing agent：0.5%th,
Accelerating agent：0.1%th,
Commercially available stock white：8.4%.
Comparative example 2
According to the preparation method of above-described embodiment 9, the stock white of embodiment 1 therein is substituted for traditional stock white
(purchased in market) as a comparison case；The dosage of component is as follows in comparative example：
UPR resins：15%th,
Filler：70%th,
Curing agent：0.5%th,
Accelerating agent：0.1%th,
Commercially available stock white：14.4%.
Performance and effect detection
The performance of the artificial stone of embodiment 7-9 and comparative example 1 is detected, detection project and result are referring to table 1.
Table 1：Performance test results
As shown in Table 1, stock white of the invention is processed into the properties after artificial stone and is superior to using tradition
The artificial stone of commercially available stock white, the performance of the obtained artificial stone of the present invention are influenced smaller by the additive amount of stock white；And
When the dosage increase of commercially available stock white, the mechanical performance of artificial stone is a greater impact the results show in comparative example.
It will be apparent to those skilled in the art that can technical solution and design as described above, make other various phases
The change and deformation answered, and all these change and deformation should all belong to the claims in the present invention protection domain it
It is interior.
Claims (10)
1. a kind of unsaturated-resin for artificial stone, which is characterized in that preparing the raw material of modified unsaturated resin includes
Cis-1, tetrahydrophthalic anhydride as acid starting material；
Propylene glycol, diethylene glycol and neopentyl glycol as raw polyol；
Wherein acid-alcohol ratio is 1:Mole total amount of (1-1.1), propylene glycol and diethylene glycol and the molar ratio of neopentyl glycol are
(0.80-0.95):0.1；
Further include styrene and polymerization inhibitor, the styrene dosage is acid starting material and the 30%-33% of raw polyol gross mass, described
Polymerization inhibitor is acid starting material and raw polyol gross mass 0.01-0.05%.
2. as described in claim 1 be used for artificial stone unsaturated-resin, which is characterized in that the cis-1 and
The molar ratio of tetrahydrophthalic anhydride is 1:1, the molar ratio of the propylene glycol and diethylene glycol is 1:1.
3. a kind of preparation method of the unsaturated-resin as described in claim 1 for artificial stone, which is characterized in that including
Step of esterification：Nitrogen will be passed through in reaction kettle, be added to cis-1 and tetrahydrophthalic anhydride according to proportioning
In reaction kettle, it is added to after then mixing propylene glycol, diethylene glycol and neopentyl glycol by pipeline in reaction kettle, to reaction kettle
It is heated, the agitating paddle that reaction kettle is started during reactor temperature is raised is stirred material reaction, simultaneously
Heating temperature is controlled, when the temperature of charge in reaction kettle reaches 160 DEG C, when insulation reaction 1-2 is small, then proceedes to be warming up to
210 DEG C, stop heating after the completion of reaction, obtain carboxylate；
Modified-reaction step：Styrene is added to by pipeline in the thinning vessel after having used nitrogen or vacuumize process, is added in
Polymerization inhibitor；When above-mentioned carboxylate is cooled to 140-150 DEG C, the carboxylate of reaction kettle is added slowly to thinning vessel with negative pressure
In, control the temperature of thinning vessel below 85 DEG C, stir thinning vessel in material to material be cooled to less than 48 DEG C, obtain partly into
Product；
Filtration step：After above-mentioned semi-finished product are filtered, finished product is obtained.
4. the preparation method of the unsaturated-resin of artificial stone to be used for as claimed in claim 3, which is characterized in that the esterification is anti-
It answers in step, reaction kettle is heated using 220-240 DEG C of conduction oil.
5. the preparation method of the unsaturated-resin for artificial stone as described in claim 3 or 4, which is characterized in that further include
Be detected before carboxylate is transferred to thinning vessel to the viscosity and acid value of carboxylate the step of, the detection of viscosimeter acidity reaches pre-
Definite value stops heating.
6. a kind of artificial stone stock white, which is characterized in that including titanium dioxide and unsaturated-resin described in claim 1, wherein
The mass percent of titanium dioxide and unsaturated-resin is respectively 20-50% and 50-80%.
7. artificial stone stock white as claimed in claim 6, which is characterized in that the mass ratio of the titanium dioxide and unsaturated-resin
For 1：3.
8. a kind of artificial stone, which is characterized in that including the following components being calculated in mass percent：
Resin：8-15%,
Filler：70-80%,
Curing agent：0.5-1.5%,
Accelerating agent：0.05-0.1%,
Stock white described in claim 6：10-18%.
9. artificial stone according to claim 8, which is characterized in that the resin is UPR resins or described in claim 1
Unsaturated-resin.
10. artificial stone according to claim 8, which is characterized in that the filler is CaCO3、MgO、Al(OH)3In one
It is mixed above in kind or amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN110668732A (en) * | 2019-10-24 | 2020-01-10 | 广东河源住方高分子材料有限公司 | Ultra-white fine particle quartz stone plate and forming method thereof |
| CN113402701A (en) * | 2021-07-06 | 2021-09-17 | 江阴市建恒化工有限公司 | Unsaturated polyester resin and preparation method thereof |
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Application publication date: 20180518 |