CN108192308A - A kind of corrosion-resistant unsaturated polyester resin and preparation method thereof - Google Patents
A kind of corrosion-resistant unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN108192308A CN108192308A CN201711486243.0A CN201711486243A CN108192308A CN 108192308 A CN108192308 A CN 108192308A CN 201711486243 A CN201711486243 A CN 201711486243A CN 108192308 A CN108192308 A CN 108192308A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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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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- 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
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
Abstract
The invention discloses a kind of corrosion-resistant unsaturated polyester resins, belong to resin making technique field, the corrosion-resistant unsaturated polyester resin, including following raw material：Unsaturated polyester resin, organic siliconresin, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl oxygen second tin, isophthalic anhydride, three fulminuric acid fat, makrolon, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second tin, Hexafluorobutyl mathacrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake, cellulose acetate, zinc acetate, silane coupling agent KH 560, corrosion-resistant modified additive, the corrosion-resistant unsaturated polyester resin is by preparing base-material, prepare modified materials, and by base-material, the materials such as modified materials mixing and etc. made of.The unsaturated polyester resin that the present invention is prepared has excellent corrosion resistance.
Description
Technical field
The present invention relates to the technical field of resin preparation process more particularly to a kind of corrosion-resistant unsaturated polyester resin and its
Preparation method.
Background technology
Unsaturated polyester (UP) is a kind of mature, industrialized thermosetting resin, and corresponding product is in laminate, Building wood
Material, adhesive, coating, construction industry and power industry are used widely.Unsaturated polyester (UP) raw material sources are wide, of low cost；
Normal temperature solidified molding, hardening time is controllable, and moulding process is simple；Product surface light is plentiful after curing, hardness is high, wearability
Good, electrical property and against weather are excellent.Although unsaturated polyester (UP) possesses many advantages, there is also some defects.Such as tradition not
Saturated polyester material is usually all more crisp, poor toughness, inflammable and not acidproof, caustic corrosion.
A kind of Chinese patent application document " unsaturated polyester resin and preparation method thereof (application publication number：
CN102532424A a kind of unsaturated polyester resin and preparation method thereof) " is disclosed, raw material components mass percent is benzene second
Alkene is 10-35%, and polymerization inhibitor 0.001-0.01%, auxiliary agent 0.01-0.05%, polyester is surplus：By dihydric alcohol and binary acid
Through 210-220 DEG C of pyroreaction, esterification dehydration, the polyester of generation mixes again with styrene, add auxiliary agent and polymerization inhibitor to get
Unsaturated polyester resin, the unsaturated polyester resin can provide the brightness of resin surface, abrasion and impact strength, can
Applied in a variety of chemical fields.But the corrosion resistance of the unsaturated polyester resin can not meet need in actual use
It asks.
Invention content
To solve technical problem present in background technology, the present invention propose a kind of corrosion-resistant unsaturated polyester resin and its
Preparation method, to solve in a kind of Chinese patent application document " unsaturated polyester resin and preparation method thereof (application publication number：
CN102532424A the problem of unsaturated polyester resin corrosion resistance is insufficient disclosed in) ".
A kind of corrosion-resistant unsaturated polyester resin proposed by the present invention, including following raw material：It is unsaturated polyester resin, organic
Silicones, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl oxygen second tin, isophthalic anhydride, three fulminuric acids
Fat, makrolon, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second
Tin, Hexafluorobutyl mathacrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake, acetic acid
Cellulose, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive；
The cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive weight ratio be (8-
14)：(6-9)：(2-4)：(18-26).
Further, the weight of the cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive
Than being 11：7.5：3：22.
Further, as unit of parts by weight, including following raw material：80-120 parts of unsaturated polyester resin, organosilicon tree
4-8 parts of fat, 3-9 parts of trimethyl phosphate, 2-6 parts of alkyd resin, 4-8 parts of dicyclopentadiene, 3-9 parts of dibutyl oxygen second tin, isophthalic
2-6 parts of dicarboxylic acid anhydride, 1-5 parts of three fulminuric acid fat, 3-6 parts of makrolon, 1-5 parts of cobalt iso-octoate, 4-8 parts of ring valeric acid cobalt,
3-6 parts of Hexafluorobutyl mathacrylate, 1-5 parts of methyl ethyl ketone peroxide, 3-6 parts of oleic acid, 4-8 parts of dibutyl oxygen second tin, methyl-prop
3-9 parts of olefin(e) acid hexafluoro butyl ester, 2-5 parts of trimethylolpropane allyl ether, 1-5 parts of castor oil, 4-8 parts of blanc fixe, glass
2-6 parts of glass scale, 8-14 parts of cellulose acetate, 6-9 parts of zinc acetate, KH-5602-4 parts of silane coupling agent, corrosion-resistant modified additive
18-26 parts.
Further, the raw material of the corrosion-resistant modified additive includes by weight：4-8 parts of phenolic resin, rare earth chloride
3-5 parts, 2-6 parts of methacrylate, 1-5 parts of alkyl phenol polyoxyethylene ether, 4-6 parts of ammonium persulfate, 2-6 parts of ethyl orthosilicate,
1-5 parts of nano aluminum nitride, 4-8 parts of lightweight calcium activated, 3-6 parts of glacial acetic acid, 2-5 parts of Silane coupling reagent KH-570, nanometer titanium dioxide
1-6 parts of titanium.
Further, the corrosion-resistant modified additive is prepared by following technique：Phenolic resin is added in into rare earth chloride
In be uniformly mixed, be warming up to 60-80 DEG C, keep the temperature 10-30min, kept stirring during heat preservation, then proceed to be warming up to 80-
90 DEG C, 10-15min is kept the temperature, is then refluxed for 3-4h, then vacuum dehydration, then heat to 140-160 DEG C, keep the temperature 5-15min,
It is cooled to room temperature to obtain material a；By material a, methacrylate, alkyl phenol polyoxyethylene ether, ammonium persulfate, positive silicic acid second
Ester, nano aluminum nitride, lightweight calcium activated and glacial acetic acid are uniformly mixed, and are warming up to 28-32 DEG C, are kept the temperature 0.5-1.5h, are then added in
Silane coupling reagent KH-570 and nano-titanium dioxide are uniformly mixed, and are warming up to 45-66 DEG C, are kept the temperature 1-3h, are vacuumized drying, are cooled down
Corrosion-resistant modified additive is obtained to room temperature.
The present invention also provides a kind of preparation methods of corrosion-resistant unsaturated polyester resin, include the following steps：
S1, by unsaturated polyester resin, organic siliconresin, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl
Oxygen second tin, isophthalic anhydride, three fulminuric acid fat are uniformly mixed, and are warming up to 70-80 DEG C, keep the temperature 20-30min, are then added
Enter makrolon, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second
Tin, Hexafluorobutyl mathacrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake mixing are equal
It is even, 70-80 DEG C is continuously heating to, keeps the temperature 30-50min, then 10-20min is stirred in 350-450r/min rotating speeds, is cooled to room
Temperature obtains base-material；
S2, cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive are uniformly mixed, are warming up to
80-90 DEG C, 20-40min is kept the temperature, then 5-15min is stirred in 1500-2500r/min rotating speeds, is cooled to room temperature and is modified
Material；
S3, base-material is warming up to 60-80 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials and be uniformly mixed, in 1200-
1400r/min rotating speeds stir 2-4h, are cooled to room temperature to obtain corrosion-resistant unsaturated polyester resin.
The invention has the advantages that：
(1) by the data of embodiment 1-3 and comparative example 6 as it can be seen that using the corrosion-resistant unsaturated polyester resins of embodiment 1-3
Corrosion resistance significantly improves；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-5 as it can be seen that cellulose acetate, zinc acetate, silane coupling agent KH-560,
Corrosion-resistant modified additive adds synergistic effect is played in corrosion-resistant unsaturated polyester resin is prepared simultaneously, significantly improves resistance to
Corrode the corrosion resistance of unsaturated polyester resin, this may be：It is cellulose acetate, zinc acetate, silane coupling agent KH-560, resistance to
Corrosion modified additive is applied to as modified system in the preparation of unsaturated polyester resin, is utilized silane coupling agent KH-560's
Graft modification acts on, and realizes cellulose acetate, zinc acetate and the hydroxyl on corrosion-resistant modified additive surface and unsaturated polyester (UP) tree
The base-material of fat realizes grafting, imparts the excellent corrosion resistance of unsaturated polyester resin, while corrosion-resistant modification is utilized and helps
The corrosion-resistant humidification of agent wherein corrosion-resistant modified additive is uniformly mixed by the way that phenolic resin is added in rare earth chloride, rises
Temperature, heat preservation, keeps stirring during heat preservation, then proceedes to heat up, and keeps the temperature, is then refluxed for, then vacuum dehydration, Ran Housheng
Temperature, heat preservation, is cooled to room temperature to obtain material a；By material a, methacrylate, alkyl phenol polyoxyethylene ether, ammonium persulfate, just
Silester, nano aluminum nitride, lightweight calcium activated and glacial acetic acid are uniformly mixed, and are heated up, then heat preservation adds in silane coupling agent
KH-570 and nano-titanium dioxide are uniformly mixed, and are heated up, and heat preservation vacuumizes drying, is cooled to room temperature to obtain corrosion-resistant modification and help
Agent is applied in the preparation of unsaturated polyester resin of the present invention, under the action of silane coupling agent KH-560, is realized and insatiable hunger
Grafting combination is carried out with the major ingredient of polyester resin, effectively increases the corrosion resistance of unsaturated polyester resin.
Specific embodiment
The present invention is described in detail with reference to specific embodiment, it should be appreciated that embodiment is served only for illustrating this hair
Bright rather than for limiting the invention, any modification made on the basis of the present invention, equivalent replacement etc. are in this hair
In bright protection domain.
In embodiment, the corrosion-resistant unsaturated polyester resin, as unit of parts by weight, including following raw material：Insatiable hunger
With 80-120 parts of polyester resin, 4-8 parts of organic siliconresin, 3-9 parts of trimethyl phosphate, 2-6 parts of alkyd resin, dicyclopentadiene 4-
8 parts, it is 3-9 parts of dibutyl oxygen second tin, 2-6 parts of isophthalic anhydride, 1-5 parts of three fulminuric acid fat, 3-6 parts of makrolon, different
1-5 parts of cobalt octoate, 4-8 parts of ring valeric acid cobalt, 3-6 parts of Hexafluorobutyl mathacrylate, 1-5 parts of methyl ethyl ketone peroxide, oleic acid 3-6
Part, 4-8 parts of dibutyl oxygen second tin, 3-9 parts of Hexafluorobutyl mathacrylate, 2-5 parts of trimethylolpropane allyl ether, castor-oil plant
1-5 parts oily, 4-8 parts of blanc fixe, 2-6 parts of glass flake, 8-14 parts of cellulose acetate, 6-9 parts of zinc acetate, silane coupling agent
It is 2-4 parts of KH-560, modified additive 18-26 parts corrosion-resistant.
The corrosion-resistant modified additive is prepared by following technique：4-8 parts of phenolic resin are added in 3-5 parts by weight
It is uniformly mixed in rare earth chloride, is warming up to 60-80 DEG C, kept the temperature 10-30min, kept stirring during heat preservation, then proceed to rise
Temperature keeps the temperature 10-15min, is then refluxed for 3-4h, then vacuum dehydration to 80-90 DEG C, then heats to 140-160 DEG C, keeps the temperature 5-
15min is cooled to room temperature to obtain material a；By a, 2-6 parts of methacrylates of material, 1-5 parts of alkyl phenol polyoxyethylene ether, 4-6
Part ammonium persulfate, 2-6 parts of ethyl orthosilicates, 1-5 parts of nano aluminum nitrides, 4-8 parts of lightweight calcium activateds and 3-6 parts of glacial acetic acids mixing are equal
It is even, 28-32 DEG C is warming up to, keeps the temperature 0.5-1.5h, then adds in 2-5 parts of Silane coupling reagent KH-570s and 1-6 parts of nanometer titanium dioxides
Titanium is uniformly mixed, and is warming up to 45-66 DEG C, is kept the temperature 1-3h, is vacuumized drying, be cooled to room temperature to obtain corrosion-resistant modified additive.
The preparation method of the corrosion-resistant unsaturated polyester resin, includes the following steps：
S1, by unsaturated polyester resin, organic siliconresin, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl
Oxygen second tin, isophthalic anhydride, three fulminuric acid fat are uniformly mixed, and are warming up to 70-80 DEG C, keep the temperature 20-30min, are then added
Enter makrolon, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second
Tin, Hexafluorobutyl mathacrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake mixing are equal
It is even, 70-80 DEG C is continuously heating to, keeps the temperature 30-50min, then 10-20min is stirred in 350-450r/min rotating speeds, is cooled to room
Temperature obtains base-material；
S2, cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive are uniformly mixed, are warming up to
80-90 DEG C, 20-40min is kept the temperature, then 5-15min is stirred in 1500-2500r/min rotating speeds, is cooled to room temperature and is modified
Material；
S3, base-material is warming up to 60-80 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials and be uniformly mixed, in 1200-
1400r/min rotating speeds stir 2-4h, are cooled to room temperature to obtain corrosion-resistant unsaturated polyester resin.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of corrosion-resistant unsaturated polyester resin, as unit of parts by weight, including following raw material：Unsaturated polyester resin
100 parts, 6 parts of organic siliconresin, 6 parts of trimethyl phosphate, 4 parts of alkyd resin, 6 parts of dicyclopentadiene, 6 parts of dibutyl oxygen second tin,
4 parts of isophthalic anhydride, 3 parts of three fulminuric acid fat, 4.5 parts of makrolon, 3 parts of cobalt iso-octoate, 6 parts of ring valeric acid cobalt, methyl
4.5 parts of hexafluorobutyl acrylate, 3 parts of methyl ethyl ketone peroxide, 4.5 parts of oleic acid, 6 parts of dibutyl oxygen second tin, methacrylic acid hexafluoro
6 parts of butyl ester, 3.5 parts of trimethylolpropane allyl ether, 3 parts of castor oil, 6 parts of blanc fixe, 4 parts of glass flake, acetic acid
11 parts of cellulose, 7.5 parts of zinc acetate, 3 parts of silane coupling agent KH-560,22 parts of corrosion-resistant modified additive.
The corrosion-resistant modified additive is prepared by following technique：6 parts of phenolic resin are added in into 4 parts of chlorinations by weight
It is uniformly mixed in rare earth, is warming up to 70 DEG C, kept the temperature 20min, kept stirring during heat preservation, then proceed to be warming up to 85 DEG C,
12min is kept the temperature, is then refluxed for 3.5h, then vacuum dehydration, then heats to 150 DEG C, 10min is kept the temperature, is cooled to room temperature to obtain
Material a；By material a, 4 parts of methacrylates, 3 parts of alkyl phenol polyoxyethylene ether, 5 parts of ammonium persulfates, 4 parts of ethyl orthosilicates, 3
Part nano aluminum nitride, 6 parts of lightweight calcium activateds and 4.5 parts of glacial acetic acids are uniformly mixed, and are warming up to 30 DEG C, are kept the temperature 1h, are then added in 3.5
Part Silane coupling reagent KH-570 and 3.5 parts of nano-titanium dioxides are uniformly mixed, and are warming up to 50 DEG C, are kept the temperature 2h, are vacuumized drying, cold
But corrosion-resistant modified additive is obtained to room temperature.
The preparation method of the corrosion-resistant unsaturated polyester resin, includes the following steps：
S1, by unsaturated polyester resin, organic siliconresin, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl
Oxygen second tin, isophthalic anhydride, three fulminuric acid fat are uniformly mixed, and are warming up to 75 DEG C, are kept the temperature 25min, are subsequently added into poly- carbon
Acid esters, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second tin, methyl
Hexafluorobutyl acrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake are uniformly mixed, and are continued
75 DEG C are warming up to, keeps the temperature 40min, then 15min is stirred in 400r/min rotating speeds, is cooled to room temperature to obtain base-material；
S2, cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive are uniformly mixed, are warming up to
85 DEG C, 30min is kept the temperature, then 10min is stirred in 2000r/min rotating speeds, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 70 DEG C, keeps the temperature 25min, be subsequently added into modified materials and be uniformly mixed, in 1300r/min rotating speeds
3h is stirred, is cooled to room temperature to obtain corrosion-resistant unsaturated polyester resin.
Embodiment 2
A kind of corrosion-resistant unsaturated polyester resin, as unit of parts by weight, including following raw material：Unsaturated polyester resin 80
Part, 8 parts of organic siliconresin, 3 parts of trimethyl phosphate, 6 parts of alkyd resin, 4 parts of dicyclopentadiene, 9 parts of dibutyl oxygen second tin, isophthalic
2 parts of dicarboxylic acid anhydride, 5 parts of three fulminuric acid fat, 3 parts of makrolon, 5 parts of cobalt iso-octoate, 4 parts of ring valeric acid cobalt, methacrylic acid
6 parts of hexafluoro butyl ester, 1 part of methyl ethyl ketone peroxide, 6 parts of oleic acid, 4 parts of dibutyl oxygen second tin, 9 parts of Hexafluorobutyl mathacrylate, three
2 parts of hydroxymethyl-propane diallyl ether, 5 parts of castor oil, 4 parts of blanc fixe, 6 parts of glass flake, 8 parts of cellulose acetate, vinegar
Sour 9 parts of zinc, 2 parts of silane coupling agent KH-560,26 parts of corrosion-resistant modified additive.
The corrosion-resistant modified additive is prepared by following technique：4 parts of phenolic resin are added in into 5 parts of chlorinations by weight
It is uniformly mixed in rare earth, is warming up to 60 DEG C, kept the temperature 30min, kept stirring during heat preservation, then proceed to be warming up to 80 DEG C,
15min is kept the temperature, is then refluxed for 3h, then vacuum dehydration, then heats to 160 DEG C, 5min is kept the temperature, is cooled to room temperature to obtain material
a；Material a, 6 parts of methacrylates, 1 part of alkyl phenol polyoxyethylene ether, 6 parts of ammonium persulfates, 2 parts of ethyl orthosilicates, 5 parts are received
Rice aluminium nitride, 4 parts of lightweight calcium activateds and 6 parts of glacial acetic acids are uniformly mixed, and are warming up to 28 DEG C, keep the temperature 1.5h, then add in 2 parts of silane
Coupling agent kh-570 and 6 parts of nano-titanium dioxides are uniformly mixed, and are warming up to 45 DEG C, are kept the temperature 3h, are vacuumized drying, be cooled to room temperature
Obtain corrosion-resistant modified additive.
The preparation method of the corrosion-resistant unsaturated polyester resin, includes the following steps：
S1, by unsaturated polyester resin, organic siliconresin, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl
Oxygen second tin, isophthalic anhydride, three fulminuric acid fat are uniformly mixed, and are warming up to 70 DEG C, are kept the temperature 30min, are subsequently added into poly- carbon
Acid esters, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second tin, methyl
Hexafluorobutyl acrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake are uniformly mixed, and are continued
70 DEG C are warming up to, keeps the temperature 50min, then 20min is stirred in 350r/min rotating speeds, is cooled to room temperature to obtain base-material；
S2, cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive are uniformly mixed, are warming up to
80 DEG C, 40min is kept the temperature, then 15min is stirred in 1500r/min rotating speeds, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 60 DEG C, keeps the temperature 35min, be subsequently added into modified materials and be uniformly mixed, in 1200r/min rotating speeds
4h is stirred, is cooled to room temperature to obtain corrosion-resistant unsaturated polyester resin.
Embodiment 3
A kind of corrosion-resistant unsaturated polyester resin, as unit of parts by weight, including following raw material：Unsaturated polyester resin
120 parts, 4 parts of organic siliconresin, 9 parts of trimethyl phosphate, 2 parts of alkyd resin, 8 parts of dicyclopentadiene, 3 parts of dibutyl oxygen second tin,
6 parts of isophthalic anhydride, 1 part of three fulminuric acid fat, 6 parts of makrolon, 1 part of cobalt iso-octoate, 8 parts of ring valeric acid cobalt, methyl-prop
3 parts of olefin(e) acid hexafluoro butyl ester, 5 parts of methyl ethyl ketone peroxide, 3 parts of oleic acid, 8 parts of dibutyl oxygen second tin, Hexafluorobutyl mathacrylate 3
Part, 5 parts of trimethylolpropane allyl ether, 1 part of castor oil, 8 parts of blanc fixe, 2 parts of glass flake, cellulose acetate 14
Part, 6 parts of zinc acetate, 4 parts of silane coupling agent KH-560,18 parts of corrosion-resistant modified additive.
The corrosion-resistant modified additive is prepared by following technique：8 parts of phenolic resin are added in into 3 parts of chlorinations by weight
It is uniformly mixed in rare earth, is warming up to 80 DEG C, kept the temperature 10min, kept stirring during heat preservation, then proceed to be warming up to 90 DEG C,
10min is kept the temperature, is then refluxed for 4h, then vacuum dehydration, then heats to 140 DEG C, 15min is kept the temperature, is cooled to room temperature to obtain object
Expect a；By material a, 2 parts of methacrylates, 5 parts of alkyl phenol polyoxyethylene ether, 4 parts of ammonium persulfates, 6 parts of ethyl orthosilicates, 1 part
Nano aluminum nitride, 8 parts of lightweight calcium activateds and 3 parts of glacial acetic acids are uniformly mixed, and are warming up to 32 DEG C, keep the temperature 0.5h, then add in 5 parts of silicon
Alkane coupling agent kh-570 and 1 part of nano-titanium dioxide are uniformly mixed, and are warming up to 66 DEG C, are kept the temperature 1h, are vacuumized drying, be cooled to room
Temperature obtains corrosion-resistant modified additive.
The preparation method of the corrosion-resistant unsaturated polyester resin, includes the following steps：
S1, by unsaturated polyester resin, organic siliconresin, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl
Oxygen second tin, isophthalic anhydride, three fulminuric acid fat are uniformly mixed, and are warming up to 80 DEG C, are kept the temperature 20min, are subsequently added into poly- carbon
Acid esters, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second tin, methyl
Hexafluorobutyl acrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake are uniformly mixed, and are continued
80 DEG C are warming up to, keeps the temperature 30min, then 10min is stirred in 450r/min rotating speeds, is cooled to room temperature to obtain base-material；
S2, cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive are uniformly mixed, are warming up to
90 DEG C, 20min is kept the temperature, then 5min is stirred in 2500r/min rotating speeds, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 80 DEG C, keeps the temperature 15min, be subsequently added into modified materials and be uniformly mixed, in 1400r/min rotating speeds
2h is stirred, is cooled to room temperature to obtain corrosion-resistant unsaturated polyester resin.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the original of corrosion-resistant unsaturated polyester resin
Lack cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive in material.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the original of corrosion-resistant unsaturated polyester resin
Lack cellulose acetate in material.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the original of corrosion-resistant unsaturated polyester resin
Lack zinc acetate in material.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the original of corrosion-resistant unsaturated polyester resin
Lack silane coupling agent KH-560 in material.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the original of corrosion-resistant unsaturated polyester resin
Lack corrosion-resistant modified additive in material.
Comparative example 6
Using a kind of Chinese patent application document " unsaturated polyester resin and preparation method thereof (application publication number：
CN102532424A) " technique of embodiment 1 prepares unsaturated polyester resin.
The unsaturated polyester resin for measuring embodiment 1-3 and comparative example 1-6 carries out indices detection, obtained detection knot
Fruit such as following table：
(1) by the data of embodiment 1-3 and comparative example 6 as it can be seen that using the corrosion-resistant unsaturated polyester resins of embodiment 1-3
Corrosion resistance significantly improves；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-5 as it can be seen that cellulose acetate, zinc acetate, silane coupling agent KH-560,
Corrosion-resistant modified additive adds synergistic effect is played in corrosion-resistant unsaturated polyester resin is prepared simultaneously, significantly improves resistance to
Corrode the corrosion resistance of unsaturated polyester resin, this may be：It is cellulose acetate, zinc acetate, silane coupling agent KH-560, resistance to
Corrosion modified additive is applied to as modified system in the preparation of unsaturated polyester resin, is utilized silane coupling agent KH-560's
Graft modification acts on, and realizes cellulose acetate, zinc acetate and the hydroxyl on corrosion-resistant modified additive surface and unsaturated polyester (UP) tree
The base-material of fat realizes grafting, imparts the excellent corrosion resistance of unsaturated polyester resin, while corrosion-resistant modification is utilized and helps
The corrosion-resistant humidification of agent wherein corrosion-resistant modified additive is uniformly mixed by the way that phenolic resin is added in rare earth chloride, rises
Temperature, heat preservation, keeps stirring during heat preservation, then proceedes to heat up, and keeps the temperature, is then refluxed for, then vacuum dehydration, Ran Housheng
Temperature, heat preservation, is cooled to room temperature to obtain material a；By material a, methacrylate, alkyl phenol polyoxyethylene ether, ammonium persulfate, just
Silester, nano aluminum nitride, lightweight calcium activated and glacial acetic acid are uniformly mixed, and are heated up, then heat preservation adds in silane coupling agent
KH-570 and nano-titanium dioxide are uniformly mixed, and are heated up, and heat preservation vacuumizes drying, is cooled to room temperature to obtain corrosion-resistant modification and help
Agent is applied in the preparation of unsaturated polyester resin of the present invention, under the action of silane coupling agent KH-560, is realized and insatiable hunger
Grafting combination is carried out with the major ingredient of polyester resin, effectively increases the corrosion resistance of unsaturated polyester resin.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of corrosion-resistant unsaturated polyester resin, which is characterized in that including following raw material：Unsaturated polyester resin, organosilicon
Resin, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl oxygen second tin, isophthalic anhydride, three fulminuric acid fat,
Makrolon, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second tin,
Hexafluorobutyl mathacrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake, acetate fiber
Element, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive；
The cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive weight ratio be (8-14)：(6-
9)：(2-4)：(18-26).
2. corrosion-resistant unsaturated polyester resin according to claim 1, which is characterized in that the cellulose acetate, acetic acid
Zinc, silane coupling agent KH-560, corrosion-resistant modified additive weight ratio be 11：7.5：3：22.
3. corrosion-resistant unsaturated polyester resin according to claim 1 or 2, which is characterized in that as unit of parts by weight, packet
Include following raw material：80-120 parts of unsaturated polyester resin, 4-8 parts of organic siliconresin, 3-9 parts of trimethyl phosphate, alkyd resin 2-6
Part, 3-9 parts of dibutyl oxygen second tin, 2-6 parts of isophthalic anhydride, 1-5 parts of three fulminuric acid fat, is gathered 4-8 parts of dicyclopentadiene
3-6 parts of carbonic ester, 1-5 parts of cobalt iso-octoate, 4-8 parts of ring valeric acid cobalt, 3-6 parts of Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide
1-5 parts, 3-6 parts of oleic acid, 4-8 parts of dibutyl oxygen second tin, 3-9 parts of Hexafluorobutyl mathacrylate, two allyl of trimethylolpropane
2-5 parts of base ether, 1-5 parts of castor oil, 4-8 parts of blanc fixe, 2-6 parts of glass flake, 8-14 parts of cellulose acetate, zinc acetate 6-
9 parts, it is 2-4 parts of silane coupling agent KH-560, modified additive 18-26 parts corrosion-resistant.
4. according to the corrosion-resistant unsaturated polyester resin of claim 1-3 any one of them, which is characterized in that described corrosion-resistant to change
The raw material of property auxiliary agent includes by weight：4-8 parts of phenolic resin, 3-5 parts of rare earth chloride, 2-6 parts of methacrylate, alkyl phenol
1-5 parts of polyoxyethylene ether, 4-6 parts of ammonium persulfate, 2-6 parts of ethyl orthosilicate, 1-5 parts of nano aluminum nitride, lightweight calcium activated 4-8
Part, 3-6 parts of glacial acetic acid, 2-5 parts of Silane coupling reagent KH-570,1-6 parts of nano-titanium dioxide.
5. according to the corrosion-resistant unsaturated polyester resin of claim 1-4 any one of them, which is characterized in that described corrosion-resistant to change
Property auxiliary agent is prepared by following technique：Phenolic resin is added in rare earth chloride and is uniformly mixed, is warming up to 60-80 DEG C, heat preservation
10-30min is kept stirring during heat preservation, is then proceeded to be warming up to 80-90 DEG C, is kept the temperature 10-15min, be then refluxed for 3-
4h, then vacuum dehydration then heat to 140-160 DEG C, keep the temperature 5-15min, are cooled to room temperature to obtain material a；By material a,
Methacrylate, alkyl phenol polyoxyethylene ether, ammonium persulfate, ethyl orthosilicate, nano aluminum nitride, lightweight calcium activated and ice second
Acid is uniformly mixed, and is warming up to 28-32 DEG C, keeps the temperature 0.5-1.5h, then adds in Silane coupling reagent KH-570 and nano-titanium dioxide
It is uniformly mixed, is warming up to 45-66 DEG C, keep the temperature 1-3h, vacuumize drying, be cooled to room temperature to obtain corrosion-resistant modified additive.
6. a kind of preparation method according to the corrosion-resistant unsaturated polyester resin of claim 1-5 any one of them, feature exists
In including the following steps：
S1, by unsaturated polyester resin, organic siliconresin, trimethyl phosphate, alkyd resin, dicyclopentadiene, dibutyl oxygen second
Tin, isophthalic anhydride, three fulminuric acid fat are uniformly mixed, and are warming up to 70-80 DEG C, are kept the temperature 20-30min, are subsequently added into poly-
Carbonic ester, cobalt iso-octoate, ring valeric acid cobalt, Hexafluorobutyl mathacrylate, methyl ethyl ketone peroxide, oleic acid, dibutyl oxygen second tin, first
Base hexafluorobutyl acrylate, trimethylolpropane allyl ether, castor oil, blanc fixe, glass flake are uniformly mixed, after
It is continuous to be warming up to 70-80 DEG C, 30-50min is kept the temperature, then 10-20min is stirred in 350-450r/min rotating speeds, is cooled to room temperature
To base-material；
S2, cellulose acetate, zinc acetate, silane coupling agent KH-560, corrosion-resistant modified additive are uniformly mixed, are warming up to 80-
90 DEG C, 20-40min is kept the temperature, then 5-15min is stirred in 1500-2500r/min rotating speeds, is cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 60-80 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials and be uniformly mixed, in 1200-1400r/
Min rotating speeds stir 2-4h, are cooled to room temperature to obtain corrosion-resistant unsaturated polyester resin.
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| CN109401260A (en) * | 2018-09-30 | 2019-03-01 | 濮阳市盛源石油化工（集团）有限公司 | A kind of corrosion-resistant halogen-free flameproof unsaturated polyester resin and preparation method thereof |
| CN109627734A (en) * | 2018-12-26 | 2019-04-16 | 成都其其小数科技有限公司 | For the lightweight of pesticide spraying unmanned plane shell, corrosion-resistant plastic and preparation method |
| CN110862662A (en) * | 2019-11-27 | 2020-03-06 | 唐山润峰复合材料有限公司 | High-strength high-toughness heat insulation type daylighting panel and processing technology thereof |
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| CN106674866A (en) * | 2016-12-12 | 2017-05-17 | 天长市康宁塑胶科技有限公司 | High-hardness corrosion-resistant modified plastic material |
| CN106751634A (en) * | 2016-12-05 | 2017-05-31 | 安徽富丽华化工有限公司 | A kind of fire-retardant corrosion-resistant modified unsaturated polyester resin and preparation method thereof |
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| CN106519135A (en) * | 2016-12-03 | 2017-03-22 | 安徽富丽华化工有限公司 | Modified unsaturated polyester resin with low viscosity and corrosion resistance and preparation method of modified unsaturated polyester resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109401260A (en) * | 2018-09-30 | 2019-03-01 | 濮阳市盛源石油化工（集团）有限公司 | A kind of corrosion-resistant halogen-free flameproof unsaturated polyester resin and preparation method thereof |
| CN109627734A (en) * | 2018-12-26 | 2019-04-16 | 成都其其小数科技有限公司 | For the lightweight of pesticide spraying unmanned plane shell, corrosion-resistant plastic and preparation method |
| CN110862662A (en) * | 2019-11-27 | 2020-03-06 | 唐山润峰复合材料有限公司 | High-strength high-toughness heat insulation type daylighting panel and processing technology thereof |
| CN110862662B (en) * | 2019-11-27 | 2021-08-20 | 唐山润峰复合材料有限公司 | High-strength high-toughness heat insulation type daylighting panel and processing technology thereof |
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