CN108192307A - A kind of high-fire resistance unsaturated polyester resin and preparation method thereof - Google Patents
A kind of high-fire resistance unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN108192307A CN108192307A CN201711486218.2A CN201711486218A CN108192307A CN 108192307 A CN108192307 A CN 108192307A CN 201711486218 A CN201711486218 A CN 201711486218A CN 108192307 A CN108192307 A CN 108192307A
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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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K2003/2227—Oxides; Hydroxides of metals of 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
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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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- 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
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- 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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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a kind of high-fire resistance unsaturated polyester resins, belong to resin making technique field, the high-fire resistance unsaturated polyester resin, including following raw material：Unsaturated polyester resin, phenolic resin, maleic anhydride, ammonium polyphosphate, phosphate melamine, isophthalic anhydride, methyl methacrylate, hydroxyethyl methacrylate, maleic anhydride, cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1, 2 propylene glycol, nano silicon dioxide, silicon carbide, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin dilaurate, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH 560, heat resistance modified auxiliary agent, the high-fire resistance 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 heat resistance.
Description
Technical field
The present invention relates to the technical field of resin preparation process more particularly to a kind of high-fire resistance unsaturated polyester resin and
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 heat resistance of unsaturated polyester resin the needs of can not meeting in actual use.
Invention content
To solve technical problem present in background technology, the present invention propose a kind of high-fire resistance unsaturated polyester resin and
Preparation method, to solve in a kind of Chinese patent application document " unsaturated polyester resin and preparation method thereof (Shen Qing Publication
Number：CN102532424A the problem of unsaturated polyester resin heat resistance is insufficient disclosed in) ".
A kind of high-fire resistance unsaturated polyester resin proposed by the present invention, including following raw material：Unsaturated polyester resin, phenol
Urea formaldehyde, maleic anhydride, ammonium polyphosphate, phosphate melamine, isophthalic anhydride, methyl methacrylate, methyl
Hydroxy-ethyl acrylate, maleic anhydride, cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1,2-PD, nanometer two
Silica, silicon carbide, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin
Cinnamic acid tin, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent；
The magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent weight ratio be (6-
8)：(8-12)：(1-3)：(15-25).
Further, the weight of the magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent
Amount is than being 7：10：2：20.
Further, as unit of parts by weight, including following raw material：80-120 parts of unsaturated polyester resin, phenolic resin
15-35 parts, 4-8 parts of maleic anhydride, 3-9 parts of ammonium polyphosphate, 2-6 parts of phosphate melamine, isophthalic anhydride 2-8
Part, 4-9 parts of methyl methacrylate, 3-9 parts of hydroxyethyl methacrylate, 2-6 parts of maleic anhydride, cumyl peroxide 1-5
Part, 4-8 parts of isocyanic acid zinc, 3-9 parts of nano-titanium dioxide, 2-8 parts of 1,2-PD, 3-6 parts of nano silicon dioxide, silicon carbide 4-
8 parts, 3-6 parts of glass fibre, 2-6 parts of zinc oxide, 1-5 parts of talcum powder, 3-6 parts of expansible graphite, 4-8 parts of hydroxy silicon oil, cycloalkanes
Sour cobalt 4-9 parts, 2-6 parts of dibutyl tin dilaurate, 6-8 parts of magnesium hydroxide, 8-12 parts of nano-aluminum hydroxide, silane coupling agent
It is 1-3 parts of KH-560, auxiliary agent 15-25 parts heat resistance modified.
Further, the raw material of the heat resistance modified auxiliary agent includes by weight：4-8 parts of carbamate, acrylic acid fourth
6-9 parts of ester, 2-6 parts of Kynoar, 1-5 parts of polypropylene, 3-9 parts of Silane coupling reagent KH-570,4-8 parts of potassium peroxydisulfate, peroxide
Change 3-9 parts of benzoyl, 2-5 parts of polyphosphoric acids aluminium, 1-5 parts of zinc borate, 4-8 parts of wood fibre, 3-9 parts of Vitrified powder, antimony trioxide
2-5 parts, 1-5 parts of zinc benzenephosphonic acid.
Further, the heat resistance modified auxiliary agent is prepared by following technique：By carbamate, butyl acrylate and
Kynoar is uniformly mixed, and then heats to 60-80 DEG C, is kept the temperature 20-40min, is subsequently added into polypropylene, silane coupling agent
KH-570, potassium peroxydisulfate, benzoyl peroxide and polyphosphoric acids aluminium are uniformly mixed, and 10- is stirred in 650-850r/min rotating speeds
30min adjusts pH to 3.5-5.0, then heats to 65-75 DEG C, keeps the temperature 0.5-1.5h, dry in 65-75 DEG C in vacuum after washing
It is dry to be cooled to room temperature to constant weight, it is equal then to add in zinc borate, wood fibre, Vitrified powder, antimony trioxide and the mixing of zinc benzenephosphonic acid
It is even, 10-20min is stirred in 80-120r/min rotating speeds, is warming up to 150-160 DEG C, 10-20min is kept the temperature, is cooled to room temperature to obtain
Heat resistance modified auxiliary agent.
The present invention also provides a kind of preparation methods of high-fire resistance unsaturated polyester resin, include the following steps：
S1, by unsaturated polyester resin, phenolic resin, maleic anhydride, ammonium polyphosphate, phosphate melamine,
Phthalate anhydride, methyl methacrylate, hydroxyethyl methacrylate, maleic anhydride are uniformly mixed, and are warming up to 70-80 DEG C, are protected
Warm 20-30min is subsequently added into cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1,2-PD, nanometer titanium dioxide
Silicon, silicon carbide, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin cinnamic acid
Tin is uniformly mixed, and is continuously heating to 70-80 DEG C, keeps the temperature 30-50min, then stirs 10-20min in 350-450r/min rotating speeds,
It is cooled to room temperature to obtain base-material；
S2, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent are uniformly mixed, heated 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 high-fire resistance 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 resistance to of embodiment 1-3 heat resistant unsaturated polyester resins
Hot property 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 magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-
560th, heat resistance modified auxiliary agent adds synergistic effect is played in heat resistant unsaturated polyester resin is prepared simultaneously, significantly improves resistance to
The heat resistance of hot unsaturated polyester resin, this may be：It is magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, resistance to
Heat modification auxiliary agent is applied to as modified system in the preparation of unsaturated polyester resin, and connecing for silane coupling agent KH-560 is utilized
Branch modifying function, realizes magnesium hydroxide, nano-aluminum hydroxide and the hydroxyl on heat resistance modified auxiliary agent surface and unsaturated polyester (UP) tree
The base-material of fat realizes grafting, imparts the excellent heat resistance of unsaturated polyester resin, while heat resistance modified auxiliary agent is utilized
Resistance to thermal enhancement, wherein heat resistance modified auxiliary agent is by the way that carbamate, butyl acrylate and Kynoar are uniformly mixed,
Then it heats up, keeps the temperature, be subsequently added into polypropylene, Silane coupling reagent KH-570, potassium peroxydisulfate, 9 parts of benzoyl peroxides and more than 2 parts
Poly aluminium phosphate is uniformly mixed, and in stirring, is adjusted pH, is then heated up, keeps the temperature, and is cooled in vacuum in drying to constant weight after washing
Then room temperature adds in zinc borate, wood fibre, Vitrified powder, antimony trioxide and zinc benzenephosphonic acid and is uniformly mixed, stirs, heat up, protect
Temperature is cooled to room temperature to obtain heat resistance modified auxiliary agent, apply in the preparation of unsaturated polyester resin of the present invention, in silane coupling agent
Under the action of KH-560, realize and carry out grafting with the major ingredient of unsaturated polyester resin and combined, effectively increase unsaturated polyester (UP)
The heat resistance of 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 high-fire resistance unsaturated polyester resin, as unit of parts by weight, including following raw material：No
80-120 parts of saturated polyester resin, 15-35 parts of phenolic resin, 4-8 parts of maleic anhydride, 3-9 parts of ammonium polyphosphate, phosphate three
2-6 parts of poly cyanamid, 2-8 parts of isophthalic anhydride, 4-9 parts of methyl methacrylate, 3-9 parts of hydroxyethyl methacrylate, Malaysia
2-6 parts of acid anhydrides, 1-5 parts of cumyl peroxide, 4-8 parts of isocyanic acid zinc, 3-9 parts of nano-titanium dioxide, 1,2-PD 2-8
Part, may expand 3-6 parts of nano silicon dioxide, 4-8 parts of silicon carbide, 3-6 parts of glass fibre, 2-6 parts of zinc oxide, 1-5 parts of talcum powder
3-6 parts of graphite, 4-9 parts of cobalt naphthenate, 2-6 parts of dibutyl tin dilaurate, 6-8 parts of magnesium hydroxide, is received 4-8 parts of hydroxy silicon oil
It is 8-12 parts of aluminium hydroxide of rice, 1-3 parts of silane coupling agent KH-560, auxiliary agent 15-25 parts heat resistance modified.
The heat resistance modified auxiliary agent is prepared by following technique：By weight by 4-8 parts of carbamates, 6-9 parts third
Olefin(e) acid butyl ester and 2-6 parts of Kynoar are uniformly mixed, and then heat to 60-80 DEG C, are kept the temperature 20-40min, are subsequently added into 1-5
Part polypropylene, 3-9 parts of Silane coupling reagent KH-570s, 4-8 parts of potassium peroxydisulfates, 3-9 parts of benzoyl peroxides and 2-5 parts of polyphosphoric acids
Aluminium is uniformly mixed, and is stirred 10-30min in 650-850r/min rotating speeds, is adjusted pH to 3.5-5.0, then heat to 65-75 DEG C,
Keep the temperature 0.5-1.5h, it is dry to constant weight in 65-75 DEG C in vacuum after washing, be cooled to room temperature, then add in 1-5 parts of zinc borates,
4-8 parts of wood fibres, 3-9 parts of Vitrified powders, 2-5 parts of antimony trioxides and 1-5 parts of zinc benzenephosphonic acids are uniformly mixed, in 80-120r/min
Rotating speed stirs 10-20min, is warming up to 150-160 DEG C, keeps the temperature 10-20min, is cooled to room temperature to obtain heat resistance modified auxiliary agent.
The preparation method of the high-fire resistance unsaturated polyester resin, includes the following steps：
S1, by unsaturated polyester resin, phenolic resin, maleic anhydride, ammonium polyphosphate, phosphate melamine,
Phthalate anhydride, methyl methacrylate, hydroxyethyl methacrylate, maleic anhydride are uniformly mixed, and are warming up to 70-80 DEG C, are protected
Warm 20-30min is subsequently added into cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1,2-PD, nanometer titanium dioxide
Silicon, silicon carbide, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin cinnamic acid
Tin is uniformly mixed, and is continuously heating to 70-80 DEG C, keeps the temperature 30-50min, then stirs 10-20min in 350-450r/min rotating speeds,
It is cooled to room temperature to obtain base-material；
S2, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent are uniformly mixed, heated 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 high-fire resistance unsaturated polyester resin.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of high-fire resistance unsaturated polyester resin, as unit of parts by weight, including following raw material：Unsaturated polyester resin
100 parts, 25 parts of phenolic resin, 6 parts of maleic anhydride, 6 parts of ammonium polyphosphate, 4 parts of phosphate melamine, isophthalic anhydride
5 parts, it is 6.5 parts of methyl methacrylate, 6 parts of hydroxyethyl methacrylate, 4 parts of maleic anhydride, 3 parts of cumyl peroxide, different
6 parts of cyanic acid zinc, 6 parts of nano-titanium dioxide, 5 parts of 1,2-PD, 4.5 parts of nano silicon dioxide, 6 parts of silicon carbide, glass fibre
4.5 parts, 4 parts of zinc oxide, 3 parts of talcum powder, 4.5 parts of expansible graphite, 6 parts of hydroxy silicon oil, 6.5 parts of cobalt naphthenate, dibutyl two
4 parts of tin laurate, 7 parts of magnesium hydroxide, 10 parts of nano-aluminum hydroxide, 2 parts of silane coupling agent KH-560, heat resistance modified auxiliary agent 20
Part.
The heat resistance modified auxiliary agent is prepared by following technique：By weight by 6 parts of carbamates, 7.5 parts of propylene
Acid butyl ester and 4 parts of Kynoar are uniformly mixed, and then heat to 70 DEG C, keep the temperature 30min, be subsequently added into 3 parts of polypropylene, 6 parts
Silane coupling reagent KH-570,6 parts of potassium peroxydisulfates, 6 parts of benzoyl peroxides and 3.5 parts of polyphosphoric acids aluminium are uniformly mixed, in 750r/
Min rotating speeds stir 20min, adjust pH to 4, then heat to 70 DEG C, keep the temperature 1h, dry to perseverance in 70 DEG C in vacuum after washing
Weight, is cooled to room temperature, and then adds in 3 parts of zinc borates, 6 parts of wood fibres, 6 parts of Vitrified powders, 3.5 parts of antimony trioxides and 3 parts of zinc benzene
Phosphoric acid is uniformly mixed, and is stirred 15min in 100r/min rotating speeds, is warming up to 155 DEG C, keeps the temperature 15min, be cooled to room temperature to obtain heat-resisting
Modified additive.
The preparation method of the high-fire resistance unsaturated polyester resin, includes the following steps：
S1, by unsaturated polyester resin, phenolic resin, maleic anhydride, ammonium polyphosphate, phosphate melamine,
Phthalate anhydride, methyl methacrylate, hydroxyethyl methacrylate, maleic anhydride are uniformly mixed, and are warming up to 75 DEG C, heat preservation
25min is subsequently added into cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1,2-PD, nano silicon dioxide, carbon
SiClx, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin dilaurate mixing
Uniformly, 75 DEG C are continuously heating to, keeps the temperature 40min, then 15min is stirred in 400r/min rotating speeds, is cooled to room temperature to obtain base-material；
S2, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent are uniformly mixed, heated 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 high-fire resistance unsaturated polyester resin.
Embodiment 2
A kind of high-fire resistance unsaturated polyester resin, as unit of parts by weight, including following raw material：Unsaturated polyester resin
80 parts, 35 parts of phenolic resin, 4 parts of maleic anhydride, 9 parts of ammonium polyphosphate, 2 parts of phosphate melamine, isophthalic anhydride 8
Part, 4 parts of methyl methacrylate, 9 parts of hydroxyethyl methacrylate, 2 parts of maleic anhydride, 5 parts of cumyl peroxide, isocyanic acid
4 parts of zinc, 9 parts of nano-titanium dioxide, 2 parts of 1,2-PD, 6 parts of nano silicon dioxide, 4 parts of silicon carbide, 6 parts of glass fibre, oxygen
Change 2 parts of zinc, 5 parts of talcum powder, 3 parts of expansible graphite, 8 parts of hydroxy silicon oil, 4 parts of cobalt naphthenate, 6 parts of dibutyl tin dilaurate,
6 parts of magnesium hydroxide, 12 parts of nano-aluminum hydroxide, 1 part of silane coupling agent KH-560,25 parts of heat resistance modified auxiliary agent.
The heat resistance modified auxiliary agent is prepared by following technique：By weight by 4 parts of carbamates, 9 parts of acrylic acid
Butyl ester and 2 parts of Kynoar are uniformly mixed, and then heat to 80 DEG C, are kept the temperature 20min, are subsequently added into 5 parts of polypropylene, 3 parts of silicon
Alkane coupling agent kh-570,8 parts of potassium peroxydisulfates, 3 parts of benzoyl peroxides and 5 parts of polyphosphoric acids aluminium are uniformly mixed, in 650r/min
Rotating speed stirs 30min, adjusts pH to 3.5, then heats to 75 DEG C, keeps the temperature 0.5h, dry to perseverance in 75 DEG C in vacuum after washing
Weight, is cooled to room temperature, and then adds in 1 part of zinc borate, 8 parts of wood fibres, 3 parts of Vitrified powders, 5 parts of antimony trioxides and 1 part of zinc benzene phosphorus
Acid is uniformly mixed, and is stirred 10min in 120r/min rotating speeds, is warming up to 160 DEG C, keeps the temperature 10min, be cooled to room temperature to obtain heat-resisting change
Property auxiliary agent.
The preparation method of the high-fire resistance unsaturated polyester resin, includes the following steps：
S1, by unsaturated polyester resin, phenolic resin, maleic anhydride, ammonium polyphosphate, phosphate melamine,
Phthalate anhydride, methyl methacrylate, hydroxyethyl methacrylate, maleic anhydride are uniformly mixed, and are warming up to 70 DEG C, heat preservation
30min is subsequently added into cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1,2-PD, nano silicon dioxide, carbon
SiClx, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin dilaurate mixing
Uniformly, 70 DEG C are continuously heating to, keeps the temperature 50min, then 20min is stirred in 350r/min rotating speeds, is cooled to room temperature to obtain base-material；
S2, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent are uniformly mixed, heated 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 high-fire resistance unsaturated polyester resin.
Embodiment 3
A kind of high-fire resistance unsaturated polyester resin, as unit of parts by weight, including following raw material：Unsaturated polyester resin
120 parts, 15 parts of phenolic resin, 8 parts of maleic anhydride, 3 parts of ammonium polyphosphate, 6 parts of phosphate melamine, isophthalic anhydride
2 parts, 9 parts of methyl methacrylate, 3 parts of hydroxyethyl methacrylate, 6 parts of maleic anhydride, 1 part of cumyl peroxide, isocyanide
Sour 8 parts of zinc, 3 parts of nano-titanium dioxide, 8 parts of 1,2-PD, 3 parts of nano silicon dioxide, 8 parts of silicon carbide, 3 parts of glass fibre,
6 parts of zinc oxide, 1 part of talcum powder, 6 parts of expansible graphite, 4 parts of hydroxy silicon oil, 9 parts of cobalt naphthenate, dibutyl tin dilaurate 2
Part, 8 parts of magnesium hydroxide, 8 parts of nano-aluminum hydroxide, 3 parts of silane coupling agent KH-560,15 parts of heat resistance modified auxiliary agent.
The heat resistance modified auxiliary agent is prepared by following technique：By weight by 8 parts of carbamates, 6 parts of acrylic acid
Butyl ester and 6 parts of Kynoar are uniformly mixed, and then heat to 60 DEG C, are kept the temperature 40min, are subsequently added into 1 part of polypropylene, 9 parts of silicon
Alkane coupling agent kh-570,4 parts of potassium peroxydisulfates, 9 parts of benzoyl peroxides and 2 parts of polyphosphoric acids aluminium are uniformly mixed, in 850r/min
Rotating speed stirs 10min, adjusts pH to 5.0, then heats to 65 DEG C, keeps the temperature 1.5h, dry to perseverance in 65 DEG C in vacuum after washing
Weight, is cooled to room temperature, and then adds in 5 parts of zinc borates, 4 parts of wood fibres, 9 parts of Vitrified powders, 2 parts of antimony trioxides and 5 parts of zinc benzene phosphorus
Acid is uniformly mixed, and is stirred 20min in 80r/min rotating speeds, is warming up to 150 DEG C, keeps the temperature 20min, be cooled to room temperature to obtain heat-resisting change
Property auxiliary agent.
The preparation method of the high-fire resistance unsaturated polyester resin, includes the following steps：
S1, by unsaturated polyester resin, phenolic resin, maleic anhydride, ammonium polyphosphate, phosphate melamine,
Phthalate anhydride, methyl methacrylate, hydroxyethyl methacrylate, maleic anhydride are uniformly mixed, and are warming up to 80 DEG C, heat preservation
20min is subsequently added into cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1,2-PD, nano silicon dioxide, carbon
SiClx, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin dilaurate mixing
Uniformly, 80 DEG C are continuously heating to, keeps the temperature 30min, then 10min is stirred in 450r/min rotating speeds, is cooled to room temperature to obtain base-material；
S2, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent are uniformly mixed, heated 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 high-fire resistance 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 high-fire resistance unsaturated polyester resin
Lack magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent in raw material.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing high-fire resistance unsaturated polyester resin
Lack magnesium hydroxide in raw material.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing high-fire resistance unsaturated polyester resin
Lack nano-aluminum hydroxide in raw material.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing high-fire resistance unsaturated polyester resin
Lack silane coupling agent KH-560 in raw material.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing high-fire resistance unsaturated polyester resin
Lack heat resistance modified auxiliary agent in raw 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 resistance to of embodiment 1-3 heat resistant unsaturated polyester resins
Hot property 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 magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-
560th, heat resistance modified auxiliary agent adds synergistic effect is played in heat resistant unsaturated polyester resin is prepared simultaneously, significantly improves resistance to
The heat resistance of hot unsaturated polyester resin, this may be：It is magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, resistance to
Heat modification auxiliary agent is applied to as modified system in the preparation of unsaturated polyester resin, and connecing for silane coupling agent KH-560 is utilized
Branch modifying function, realizes magnesium hydroxide, nano-aluminum hydroxide and the hydroxyl on heat resistance modified auxiliary agent surface and unsaturated polyester (UP) tree
The base-material of fat realizes grafting, imparts the excellent heat resistance of unsaturated polyester resin, while heat resistance modified auxiliary agent is utilized
Resistance to thermal enhancement, wherein heat resistance modified auxiliary agent is by the way that carbamate, butyl acrylate and Kynoar are uniformly mixed,
Then it heats up, keeps the temperature, be subsequently added into polypropylene, Silane coupling reagent KH-570, potassium peroxydisulfate, 9 parts of benzoyl peroxides and more than 2 parts
Poly aluminium phosphate is uniformly mixed, and in stirring, is adjusted pH, is then heated up, keeps the temperature, and is cooled in vacuum in drying to constant weight after washing
Then room temperature adds in zinc borate, wood fibre, Vitrified powder, antimony trioxide and zinc benzenephosphonic acid and is uniformly mixed, stirs, heat up, protect
Temperature is cooled to room temperature to obtain heat resistance modified auxiliary agent, apply in the preparation of unsaturated polyester resin of the present invention, in silane coupling agent
Under the action of KH-560, realize and carry out grafting with the major ingredient of unsaturated polyester resin and combined, effectively increase unsaturated polyester (UP)
The heat resistance of 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 high-fire resistance unsaturated polyester resin, which is characterized in that including following raw material：Unsaturated polyester resin, phenolic aldehyde
Resin, maleic anhydride, ammonium polyphosphate, phosphate melamine, isophthalic anhydride, methyl methacrylate, methyl-prop
Olefin(e) acid hydroxyl ethyl ester, maleic anhydride, cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1,2-PD, nano-silica
SiClx, silicon carbide, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin osmanthus
Sour tin, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent；
The magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent weight ratio be (6-8)：
(8-12)：(1-3)：(15-25).
2. high-fire resistance unsaturated polyester resin according to claim 1, which is characterized in that the magnesium hydroxide, nanometer
Aluminium hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent weight ratio be 7：10：2：20.
3. high-fire resistance unsaturated polyester resin according to claim 1 or 2, which is characterized in that as unit of parts by weight,
Including following raw material：80-120 parts of unsaturated polyester resin, 15-35 parts of phenolic resin, 4-8 parts of maleic anhydride, polyphosphoric acid
3-9 parts of ammonium, 2-6 parts of phosphate melamine, 2-8 parts of isophthalic anhydride, 4-9 parts of methyl methacrylate, methacrylic acid
3-9 parts of hydroxyl ethyl ester, 2-6 parts of maleic anhydride, 1-5 parts of cumyl peroxide, 4-8 parts of isocyanic acid zinc, nano-titanium dioxide 3-9
Part, slides 2-8 parts of 1,2-PD, 3-6 parts of nano silicon dioxide, 4-8 parts of silicon carbide, 3-6 parts of glass fibre, 2-6 parts of zinc oxide
1-5 parts of mountain flour, 3-6 parts of expansible graphite, 4-8 parts of hydroxy silicon oil, 4-9 parts of cobalt naphthenate, 2-6 parts of dibutyl tin dilaurate,
It is 6-8 parts of magnesium hydroxide, 8-12 parts of nano-aluminum hydroxide, 1-3 parts of silane coupling agent KH-560, auxiliary agent 15-25 parts heat resistance modified.
4. according to claim 1-3 any one of them high-fire resistance unsaturated polyester resins, which is characterized in that described heat-resisting to change
The raw material of property auxiliary agent includes by weight：4-8 parts of carbamate, 6-9 parts of butyl acrylate, 2-6 parts of Kynoar, poly- third
1-5 parts of alkene, 3-9 parts of Silane coupling reagent KH-570,4-8 parts of potassium peroxydisulfate, 3-9 parts of benzoyl peroxide, polyphosphoric acids aluminium 2-5
Part, 1-5 parts of zinc borate, 4-8 parts of wood fibre, 3-9 parts of Vitrified powder, 2-5 parts of antimony trioxide, 1-5 parts of zinc benzenephosphonic acid.
5. according to claim 1-4 any one of them high-fire resistance unsaturated polyester resins, which is characterized in that described heat-resisting to change
Property auxiliary agent is prepared by following technique：Carbamate, butyl acrylate and Kynoar are uniformly mixed, then heated up
To 60-80 DEG C, 20-40min is kept the temperature, is subsequently added into polypropylene, Silane coupling reagent KH-570, potassium peroxydisulfate, benzoyl peroxide
It is uniformly mixed with polyphosphoric acids aluminium, stirs 10-30min in 650-850r/min rotating speeds, adjust pH to 3.5-5.0, then heat up
To 65-75 DEG C, 0.5-1.5h is kept the temperature, it is dry to constant weight in 65-75 DEG C in vacuum after washing, it is cooled to room temperature, then adds in boron
Sour zinc, wood fibre, Vitrified powder, antimony trioxide and zinc benzenephosphonic acid are uniformly mixed, and 10- is stirred in 80-120r/min rotating speeds
20min is warming up to 150-160 DEG C, keeps the temperature 10-20min, is cooled to room temperature to obtain heat resistance modified auxiliary agent.
6. a kind of preparation method according to claim 1-5 any one of them high-fire resistance unsaturated polyester resins, feature
It is, includes the following steps：
S1, by unsaturated polyester resin, phenolic resin, maleic anhydride, ammonium polyphosphate, phosphate melamine, isophthalic two
Formic anhydride, methyl methacrylate, hydroxyethyl methacrylate, maleic anhydride are uniformly mixed, and are warming up to 70-80 DEG C, keep the temperature 20-
30min is subsequently added into cumyl peroxide, isocyanic acid zinc, nano-titanium dioxide, 1,2-PD, nano silicon dioxide, carbon
SiClx, glass fibre, zinc oxide, talcum powder, expansible graphite, hydroxy silicon oil, cobalt naphthenate, dibutyl tin dilaurate mixing
Uniformly, 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, magnesium hydroxide, nano-aluminum hydroxide, silane coupling agent KH-560, heat resistance modified auxiliary agent 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 high-fire resistance unsaturated polyester resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109486143A (en) * | 2018-10-29 | 2019-03-19 | 安徽汇创新材料有限公司 | A kind of septic tank heat resistant glass Steel material |
| GB2579652A (en) * | 2018-12-10 | 2020-07-01 | Synthomer Uk Ltd | Composition |
| CN115505294A (en) * | 2022-10-10 | 2022-12-23 | 深圳市崯涛油墨科技有限公司 | Bright silver protection ink for mobile terminal glass cover plate |
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| CN105907070A (en) * | 2016-05-03 | 2016-08-31 | 宁国市力普生复合材料有限公司 | High-temperature-resistant corrosion-resistant modified unsaturated polyester resin fiberglass-reinforced plastic grille |
| CN106749947A (en) * | 2016-12-03 | 2017-05-31 | 安徽富丽华化工有限公司 | A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity and preparation method thereof |
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2017
- 2017-12-30 CN CN201711486218.2A patent/CN108192307A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105907070A (en) * | 2016-05-03 | 2016-08-31 | 宁国市力普生复合材料有限公司 | High-temperature-resistant corrosion-resistant modified unsaturated polyester resin fiberglass-reinforced plastic grille |
| CN106749947A (en) * | 2016-12-03 | 2017-05-31 | 安徽富丽华化工有限公司 | A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109486143A (en) * | 2018-10-29 | 2019-03-19 | 安徽汇创新材料有限公司 | A kind of septic tank heat resistant glass Steel material |
| GB2579652A (en) * | 2018-12-10 | 2020-07-01 | Synthomer Uk Ltd | Composition |
| CN115505294A (en) * | 2022-10-10 | 2022-12-23 | 深圳市崯涛油墨科技有限公司 | Bright silver protection ink for mobile terminal glass cover plate |
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