CN106749947A - A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity and preparation method thereof - Google Patents
A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity and preparation method thereof Download PDFInfo
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K7/00—Use of ingredients characterised by shape
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- 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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Abstract
The invention discloses a kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity, its raw material includes maleic anhydride, isophthalic anhydride, phthalic anhydride, ethyl acetate, methyl methacrylate, benzenetriol, hydroquinones, dicyclopentadiene, cobalt naphthenate styrene, phosphate melamine, methyl ethyl ketone peroxide, cumyl peroxide, silane coupler KH 550, nano titanium oxide, nano silicon, nano-aluminum hydroxide, modified glass-fiber, TDE, silane microcapsule-coated ammonium polyphosphate, ethylene glycol, diglycol and propane diols.The present invention also proposes a kind of preparation method of the above-mentioned resistant to elevated temperatures modified unsaturated polyester resin of high tenacity.The unsaturated polyester resin that the present invention is prepared has excellent toughness and resistance to elevated temperatures.
Description
Technical field
The invention belongs to unsaturated polyester resin technical field, more particularly to a kind of resistant to elevated temperatures modified unsaturation of high tenacity
Polyester resin and preparation method thereof.
Background technology
Unsaturated polyester resin refers to have linear structure, has the one of repetition ester bond and unsaturated double-bond simultaneously on main chain
Birds of the same feather flock together compound, generally polycondensation is formed dihydroxylic alcohols at high temperature with unsaturated dibasic acid.Due to UPR have processing performance it is good,
After solidification the combination property of resin it is good, it is cheap the advantages of, have been widely used for building, ship, auto industry, track
The fields such as traffic, electrical apparatus product and light industrial products.But the resin is inflammable, is susceptible to fire, its product is caused to use
The security facing public interrogates.
The toughness and resistance to elevated temperatures of unsaturated-resin of the prior art cannot meet Anchor Agent Production requirement, therefore urgently
A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity need to be designed to solve the problems of the prior art
The content of the invention
To solve technical problem present in background technology, the present invention proposes a kind of resistant to elevated temperatures modified unsaturation of high tenacity
Polyester resin and preparation method thereof, prepare with excellent toughness and resistance to elevated temperatures.
A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity proposed by the present invention, its raw material includes by weight：
Maleic anhydride 25-35 parts, isophthalic anhydride 2-5 parts, phthalic anhydride 4-8 parts, ethyl acetate 2-5 parts, methyl-prop
E pioic acid methyl ester 1-5 parts, benzenetriol 2-6 parts, hydroquinones 3-5 parts, dicyclopentadiene 4-8 parts, 1-4 parts of cobalt naphthenate styrene,
4-8 parts of phosphate melamine, methyl ethyl ketone peroxide 3-6 parts, cumyl peroxide 1-4 parts, silane resin acceptor kh-550 2-5
Part, nano titanium oxide 3-5 parts, nano silicon 3-6 parts, nano-aluminum hydroxide 2-5 parts, modified glass-fiber 4-8 parts, ten
2-5 parts of bromine diphenylethane, 2-5 parts of silane microcapsule-coated ammonium polyphosphate, ethylene glycol 5-15 parts, diglycol 3-5 parts, third
Glycol 4-9 parts.
Preferably, modified glass-fiber is prepared by following technique：Tetrabutylammonium iodide and deionized water are mixed equal
It is even, 65-75 DEG C is then heated to, it is subsequently added into fiberglass powder and sodium hydroxide solution is well mixed, then it is warming up to 75-85
DEG C, 20-40min is incubated, watery hydrochloric acid regulation pH to 1.5-2.5 is added after filtering and washing, connect in neutrality to solution after filtering and washing
And dry 10-14h in 75-85 DEG C, be cooled to room temperature and obtain modified glass-fiber.
Preferably, in the preparation process of modified glass-fiber, tetrabutylammonium iodide, deionized water, fiberglass powder and hydrogen
The weight ratio of sodium hydroxide solution is 1-3：2-4：3-5：4-8.
Preferably, maleic anhydride, isophthalic anhydride, phthalic anhydride, ethyl acetate, methyl methacrylate
The weight ratio of ester, benzenetriol, hydroquinones, dicyclopentadiene and cobalt naphthenate styrene is 28-32：3-4：5-7：3-4：2-4：
3-5：3.5-4.5：5-7：2-3.
Preferably, methyl ethyl ketone peroxide, silane resin acceptor kh-550, nano titanium oxide, nano silicon, nanometer hydrogen
The weight ratio of aluminum oxide and modified glass-fiber is 4-5：3-4：3.5-4.5：4-5：3-4：5-7.
Preferably, the weight ratio of nano titanium oxide, TDE and silane microcapsule-coated ammonium polyphosphate is
3.5-4.5：3-4：3-4.
Preferably, its raw material includes by weight：Maleic anhydride 28-32 parts, isophthalic anhydride 3-4 parts, adjacent benzene
Dicarboxylic acid anhydride 5-7 parts, ethyl acetate 3-4 parts, methyl methacrylate 2-4 parts, benzenetriol 3-5 parts, hydroquinones 3.5-4.5
Part, dicyclopentadiene 5-7 parts, 2-3 parts of cobalt naphthenate styrene, 5-7 parts of phosphate melamine, methyl ethyl ketone peroxide 4-5 parts,
Cumyl peroxide 2-3 parts, silane resin acceptor kh-550 3-4 parts, nano titanium oxide 3.5-4.5 parts, nano silicon
4-5 parts, nano-aluminum hydroxide 3-4 parts, modified glass-fiber 5-7 parts, TDE 3-4 parts, silane microcapsule coated gather
Ammonium phosphate 3-4 parts, ethylene glycol 8-12 parts, diglycol 3.5-4.5 parts, propane diols 5-8 parts.
Preferably, its raw material includes by weight：30 parts of maleic anhydride, 3.5 parts of isophthalic anhydride, O-phthalic
6 parts of acid anhydrides, 3.5 parts of ethyl acetate, 3 parts of methyl methacrylate, 4 parts of benzenetriol, 4 parts of hydroquinones, 6 parts of dicyclopentadiene,
2.5 parts of cobalt naphthenate styrene, 6 parts of phosphate melamine, 4.5 parts of methyl ethyl ketone peroxide, 2.5 parts of cumyl peroxide,
3.5 parts of silane resin acceptor kh-550,4 parts of nano titanium oxide, 4.5 parts of nano silicon, 3.5 parts of nano-aluminum hydroxide, change
Property 6 parts of glass fibre, 3.5 parts of TDE, 3.5 parts of silane microcapsule-coated ammonium polyphosphate, 10 parts of ethylene glycol, one contracting two
4 parts of ethylene glycol, 6.5 parts of propane diols.
A kind of preparation method of the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity of the invention, comprises the following steps：
S1, ethylene glycol, diglycol, propane diols, phthalic anhydride and isophthalic anhydride are well mixed, risen
Temperature is then cooled to 150-160 DEG C to 180-220 DEG C of insulation 1-3h, adds maleic anhydride, ethyl acetate and metering system
Sour methyl esters is well mixed, and then heats to 180-190 DEG C, is incubated 2-4h, is cooled to room temperature and obtains material a；
S2, to benzenetriol is added in material a, be warming up to 195-205 DEG C, be incubated 1-3h, control vacuum for 0.1-
0.2Gpa continuously vacuumizes 1-3h control acid numbers to be stopped vacuumizing and start to be cooled to 175-185 DEG C of throwing after 20-30mgKOH/g
Enter hydroquinones to be well mixed, it is cold to go to room temperature to obtain material b；
S3, to dicyclopentadiene and cobalt naphthenate styrene is added in material b, be warming up to 125-145 DEG C, be incubated 0.5-
1.5h, then stirs 30-50min in 400-600r/min, is then cooled to 60-80 DEG C, is incubated 0.5-1.5h, is subsequently added into phosphorus
Acid esters melamine, 15-25min is stirred in 250-350r/min, is cooled to room temperature and is obtained material c；
S4, in material c add silane resin acceptor kh-550, nano titanium oxide, nano silicon, nanometer hydroxide
Aluminium, modified glass-fiber, TDE and silane microcapsule-coated ammonium polyphosphate are well mixed, in 1500-2500r/min
Stirring 30-50min, is subsequently added into cumyl peroxide and methyl ethyl ketone peroxide is well mixed, and ultrasonic disperse 10-20min is obtained
To the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity.
The resistant to elevated temperatures modified unsaturated polyester resin of a kind of high tenacity of the invention, its raw material include maleic anhydride,
Isophthalic anhydride, phthalic anhydride, ethyl acetate, methyl methacrylate, benzenetriol, hydroquinones, dicyclopentadiene,
Cobalt naphthenate styrene, phosphate melamine, methyl ethyl ketone peroxide, cumyl peroxide, silane resin acceptor kh-550, receive
Rice titanium dioxide, nano silicon, nano-aluminum hydroxide, modified glass-fiber, TDE, silane microcapsule coated
APP, ethylene glycol, diglycol and propane diols.Wherein with maleic anhydride, isophthalic anhydride and adjacent benzene two
Formic anhydride as acid reaction, using ethylene glycol, diglycol and propane diols as alcohol reactant, with ethyl acetate as molten
Agent, using methyl methacrylate as monomer additive, using benzenetriol and hydroquinones as phenols additive, with peroxidating first
Ethyl ketone is initiator, using nano titanium oxide, nano silicon, nano-aluminum hydroxide and modified glass-fiber as filler,
By silane resin acceptor kh-550 as modifying agent, using cobalt naphthenate styrene as crosslinking agent, by the insatiable hunger for preparing
There is excellent toughness and resistance to elevated temperatures with polyester resin.The modified glass-fiber for wherein adding with tetrabutylammonium iodide, go
Ionized water, fiberglass powder and sodium hydroxide solution are prepared for raw material, by sodium hydroxide solution to glass powdered steel table
Face is hydrolyzed modified, and the addition of tetrabutylammonium iodide increased the hydroxyl on glass comminuted steel shot surface, effectively increase modified
The binding ability of glass fibre and unsaturated polyester resin.Nano titanium oxide, TDE and the silane for wherein adding
Microcapsule-coated ammonium polyphosphate can effectively improve the resistance to elevated temperatures of unsaturated polyester resin of the present invention as fire retardant, fill out
Aluminium hydroxide in material also enhances the resistance to elevated temperatures of unsaturated polyester resin of the present invention simultaneously.Unsaturated polyester (UP) of the invention
Resin is applied to the preparation of Anchor Agent, and with excellent toughness and resistance to elevated temperatures, it is right in Anchor Agent preparation process to disclosure satisfy that
In the demand of excellent toughness and resistance to elevated temperatures.
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 etc. are in this hair
In bright protection domain.
In specific embodiment, the weight portion of maleic anhydride can for 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30
Part, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts；The weight portion of isophthalic anhydride can for 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4
Part, 4.5 parts, 5 parts；The weight portion of phthalic anhydride can for 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5
Part, 8 parts；The weight portion of ethyl acetate can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；Methyl methacrylate
Weight portion can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts；The weight portion of benzenetriol can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；It is right
The weight portion of benzenediol can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of dicyclopentadiene can for 4 parts, 4.5
Part, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts；The weight portion of cobalt naphthenate styrene can for 1 part, 1.5 parts, 2
Part, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The weight portion of phosphate melamine can for 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts,
6.5 parts, 7 parts, 7.5 parts, 8 parts；The weight portion of methyl ethyl ketone peroxide can for 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6
Part；The weight portion of cumyl peroxide can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；Silane coupler
The weight portion of KH-550 can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of nano titanium oxide can
Think 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of nano silicon can for 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5
Part, 5.5 parts, 6 parts；The weight portion of nano-aluminum hydroxide can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；It is modified
The weight portion of glass fibre can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts；Decabrominated dipheny second
The weight portion of alkane can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight of silane microcapsule-coated ammonium polyphosphate
Amount part can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of ethylene glycol can for 5 parts, 6 parts, 7 parts, 8
Part, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts；The weight portion of diglycol can for 3 parts, 3.5 parts, 4 parts,
4.5 parts, 5 parts；The weight portion of propane diols can for 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5
Part, 9 parts.
Embodiment 1
A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity proposed by the present invention, its raw material includes by weight：
30 parts of maleic anhydride, 3.5 parts of isophthalic anhydride, 6 parts of phthalic anhydride, 3.5 parts of ethyl acetate, methyl methacrylate
3 parts of ester, 4 parts of benzenetriol, 4 parts of hydroquinones, 6 parts of dicyclopentadiene, 2.5 parts of cobalt naphthenate styrene, phosphate melamine 6
Part, 4.5 parts of methyl ethyl ketone peroxide, 2.5 parts of cumyl peroxide, 3.5 parts of silane resin acceptor kh-550, nano titanium oxide 4
Part, 4.5 parts of nano silicon, 3.5 parts of nano-aluminum hydroxide, 6 parts of modified glass-fiber, 3.5 parts of TDE, silane
3.5 parts of microcapsule-coated ammonium polyphosphate, 10 parts of ethylene glycol, 4 parts of diglycol, 6.5 parts of propane diols.
Embodiment 2
A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity proposed by the present invention, its raw material includes by weight：
25 parts of maleic anhydride, 5 parts of isophthalic anhydride, 4 parts of phthalic anhydride, 5 parts of ethyl acetate, methyl methacrylate 1
Part, 6 parts of benzenetriol, 3 parts of hydroquinones, 8 parts of dicyclopentadiene, 1 part of cobalt naphthenate styrene, 8 parts of phosphate melamine, mistake
3 parts of MEKP, 4 parts of cumyl peroxide, 2 parts of silane resin acceptor kh-550,5 parts of nano titanium oxide, nano-silica
3 parts of SiClx, 5 parts of nano-aluminum hydroxide, 4 parts of modified glass-fiber, 5 parts of TDE, silane microcapsule coated polyphosphoric acid
2 parts of ammonium, 15 parts of ethylene glycol, 3 parts of diglycol, 9 parts of propane diols.
Modified glass-fiber is prepared by following technique：By weight by 1 part of tetrabutylammonium iodide and 4 parts of deionized waters
It is well mixed, 65 DEG C are then heated to, it is subsequently added into 5 parts of fiberglass powders and 4 parts of sodium hydroxide solutions is well mixed, then rise
Temperature is incubated 20min to 85 DEG C, and watery hydrochloric acid regulation pH to 2.5 is added after filtering and washing, is connect in neutrality to solution after filtering and washing
And dry 14h in 75 DEG C, be cooled to room temperature and obtain modified glass-fiber.
A kind of preparation method of the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity of the invention, comprises the following steps：
S1, ethylene glycol, diglycol, propane diols, phthalic anhydride and isophthalic anhydride are well mixed, risen
Temperature is then cooled to 150 DEG C to 180 DEG C of insulation 3h, adds the mixing of maleic anhydride, ethyl acetate and methyl methacrylate
Uniformly, 190 DEG C are then heated to, 2h is incubated, room temperature is cooled to and is obtained material a；
S2, to benzenetriol is added in material a, be warming up to 205 DEG C, be incubated 1h, control vacuum to be taken out very for 0.2Gpa is continuous
It is well mixed that empty 1h control acid number stops vacuumizing and start being cooled to 175 DEG C of input hydroquinones after 30mgKOH/g, cold to go
Material b is obtained to room temperature；
S3, to dicyclopentadiene and cobalt naphthenate styrene is added in material b, be warming up to 145 DEG C, be incubated 0.5h, then
30min is stirred in 600r/min, 80 DEG C are then cooled to, 0.5h is incubated, phosphate melamine is subsequently added into, in 350r/min
Stirring 15min, is cooled to room temperature and obtains material c；
S4, in material c add silane resin acceptor kh-550, nano titanium oxide, nano silicon, nanometer hydroxide
Aluminium, modified glass-fiber, TDE and silane microcapsule-coated ammonium polyphosphate are well mixed, in 2500r/min stirrings
30min, is subsequently added into cumyl peroxide and methyl ethyl ketone peroxide is well mixed, and it is resistance to that ultrasonic disperse 20min obtains high tenacity
The modified unsaturated polyester resin of high temperature.
Embodiment 3
A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity proposed by the present invention, its raw material includes by weight：
35 parts of maleic anhydride, 2 parts of isophthalic anhydride, 8 parts of phthalic anhydride, 2 parts of ethyl acetate, methyl methacrylate 5
Part, 2 parts of benzenetriol, 5 parts of hydroquinones, 4 parts of dicyclopentadiene, 4 parts of cobalt naphthenate styrene, 4 parts of phosphate melamine, mistake
6 parts of MEKP, 1 part of cumyl peroxide, 5 parts of silane resin acceptor kh-550,3 parts of nano titanium oxide, nano-silica
6 parts of SiClx, 2 parts of nano-aluminum hydroxide, 8 parts of modified glass-fiber, 2 parts of TDE, silane microcapsule coated polyphosphoric acid
5 parts of ammonium, 5 parts of ethylene glycol, 5 parts of diglycol, 4 parts of propane diols.
Modified glass-fiber is prepared by following technique：By weight by 3 parts of tetrabutylammonium iodides and 2 parts of deionized waters
It is well mixed, 75 DEG C are then heated to, it is subsequently added into 3 parts of fiberglass powders and 8 parts of sodium hydroxide solutions is well mixed, then rise
Temperature is incubated 40min to 75 DEG C, and watery hydrochloric acid regulation pH to 1.5 is added after filtering and washing, is connect in neutrality to solution after filtering and washing
And dry 10h in 85 DEG C, be cooled to room temperature and obtain modified glass-fiber.
A kind of preparation method of the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity of the invention, comprises the following steps：
S1, ethylene glycol, diglycol, propane diols, phthalic anhydride and isophthalic anhydride are well mixed, risen
Temperature is then cooled to 160 DEG C to 220 DEG C of insulation 1h, adds the mixing of maleic anhydride, ethyl acetate and methyl methacrylate
Uniformly, 180 DEG C are then heated to, 4h is incubated, room temperature is cooled to and is obtained material a；
S2, to benzenetriol is added in material a, be warming up to 195 DEG C, be incubated 3h, control vacuum to be taken out very for 0.1Gpa is continuous
It is well mixed that empty 3h control acid number stops vacuumizing and start being cooled to 185 DEG C of input hydroquinones after 20mgKOH/g, cold to go
Material b is obtained to room temperature；
S3, to dicyclopentadiene and cobalt naphthenate styrene is added in material b, be warming up to 125 DEG C, be incubated 1.5h, then
50min is stirred in 400r/min, 60 DEG C are then cooled to, 1.5h is incubated, phosphate melamine is subsequently added into, in 250r/min
Stirring 25min, is cooled to room temperature and obtains material c；
S4, in material c add silane resin acceptor kh-550, nano titanium oxide, nano silicon, nanometer hydroxide
Aluminium, modified glass-fiber, TDE and silane microcapsule-coated ammonium polyphosphate are well mixed, in 1500r/min stirrings
50min, is subsequently added into cumyl peroxide and methyl ethyl ketone peroxide is well mixed, and it is resistance to that ultrasonic disperse 10min obtains high tenacity
The modified unsaturated polyester resin of high temperature.
Embodiment 4
A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity proposed by the present invention, its raw material includes by weight：
28 parts of maleic anhydride, 4 parts of isophthalic anhydride, 5 parts of phthalic anhydride, 4 parts of ethyl acetate, methyl methacrylate 2
Part, 5 parts of benzenetriol, 3.5 parts of hydroquinones, 7 parts of dicyclopentadiene, 2 parts of cobalt naphthenate styrene, 7 parts of phosphate melamine,
4 parts of methyl ethyl ketone peroxide, 3 parts of cumyl peroxide, 3 parts of silane resin acceptor kh-550, nano titanium oxide 4.5 part, nanometer
4 parts of silica, 4 parts of nano-aluminum hydroxide, 5 parts of modified glass-fiber, 4 parts of TDE, silane microcapsule coated gather
3 parts of ammonium phosphate, 12 parts of ethylene glycol, 3.5 parts of diglycol, 8 parts of propane diols.
Modified glass-fiber is prepared by following technique：By weight by 1.5 parts of tetrabutylammonium iodides and 3.5 parts go from
Sub- water is well mixed, and then heats to 68 DEG C, is subsequently added into 4.5 parts of fiberglass powders and 5 parts of sodium hydroxide solutions are well mixed,
Then 82 DEG C are warming up to, 25min is incubated, watery hydrochloric acid regulation pH to 2.2 are added after filtering and washing, in being in solution after filtering and washing
Property, 13h is then dried in 78 DEG C, it is cooled to room temperature and obtains modified glass-fiber.
A kind of preparation method of the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity of the invention, comprises the following steps：
S1, ethylene glycol, diglycol, propane diols, phthalic anhydride and isophthalic anhydride are well mixed, risen
Temperature is then cooled to 152 DEG C to 185 DEG C of insulation 2.5h, adds maleic anhydride, ethyl acetate and methyl methacrylate mixed
Close uniform, then heat to 188 DEG C, be incubated 2.5h, be cooled to room temperature and obtain material a；
S2, to benzenetriol is added in material a, be warming up to 202 DEG C, be incubated 1.5h, control vacuum continuously to be taken out for 0.18Gpa
It is well mixed that vacuum 1.5h control acid numbers stop vacuumizing and start being cooled to 178 DEG C of input hydroquinones after 28mgKOH/g,
It is cold to go to room temperature to obtain material b；
S3, to dicyclopentadiene and cobalt naphthenate styrene is added in material b, be warming up to 142 DEG C, be incubated 0.8h, then
35min is stirred in 580r/min, 78 DEG C are then cooled to, 0.8h is incubated, phosphate melamine is subsequently added into, in 320r/min
Stirring 18min, is cooled to room temperature and obtains material c；
S4, in material c add silane resin acceptor kh-550, nano titanium oxide, nano silicon, nanometer hydroxide
Aluminium, modified glass-fiber, TDE and silane microcapsule-coated ammonium polyphosphate are well mixed, in 2200r/min stirrings
35min, is subsequently added into cumyl peroxide and methyl ethyl ketone peroxide is well mixed, and it is resistance to that ultrasonic disperse 18min obtains high tenacity
The modified unsaturated polyester resin of high temperature.
Embodiment 5
A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity proposed by the present invention, its raw material includes by weight：
32 parts of maleic anhydride, 3 parts of isophthalic anhydride, 7 parts of phthalic anhydride, 3 parts of ethyl acetate, methyl methacrylate 4
Part, 3 parts of benzenetriol, 4.5 parts of hydroquinones, 5 parts of dicyclopentadiene, 3 parts of cobalt naphthenate styrene, 5 parts of phosphate melamine,
5 parts of methyl ethyl ketone peroxide, 2 parts of cumyl peroxide, 4 parts of silane resin acceptor kh-550, nano titanium oxide 3.5 part, nanometer
5 parts of silica, 3 parts of nano-aluminum hydroxide, 7 parts of modified glass-fiber, 3 parts of TDE, silane microcapsule coated gather
4 parts of ammonium phosphate, 8 parts of ethylene glycol, 4.5 parts of diglycol, 5 parts of propane diols.
Modified glass-fiber is prepared by following technique：By weight by 2.5 parts of tetrabutylammonium iodides and 2.5 parts go from
Sub- water is well mixed, and then heats to 72 DEG C, is subsequently added into 3.5 parts of fiberglass powders and 7 parts of sodium hydroxide solutions are well mixed,
Then 78 DEG C are warming up to, 35min is incubated, watery hydrochloric acid regulation pH to 1.8 are added after filtering and washing, in being in solution after filtering and washing
Property, 11h is then dried in 82 DEG C, it is cooled to room temperature and obtains modified glass-fiber.
A kind of preparation method of the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity of the invention, comprises the following steps：
S1, ethylene glycol, diglycol, propane diols, phthalic anhydride and isophthalic anhydride are well mixed, risen
Temperature is then cooled to 158 DEG C to 215 DEG C of insulation 1.5h, adds maleic anhydride, ethyl acetate and methyl methacrylate mixed
Close uniform, then heat to 182 DEG C, be incubated 3.5h, be cooled to room temperature and obtain material a；
S2, to benzenetriol is added in material a, be warming up to 198 DEG C, be incubated 2.5h, control vacuum continuously to be taken out for 0.12Gpa
It is well mixed that vacuum 2.5h control acid numbers stop vacuumizing and start being cooled to 182 DEG C of input hydroquinones after 22mgKOH/g,
It is cold to go to room temperature to obtain material b；
S3, to dicyclopentadiene and cobalt naphthenate styrene is added in material b, be warming up to 128 DEG C, be incubated 1.2h, then
45min is stirred in 420r/min, 62 DEG C are then cooled to, 1.2h is incubated, phosphate melamine is subsequently added into, in 280r/min
Stirring 22min, is cooled to room temperature and obtains material c；
S4, in material c add silane resin acceptor kh-550, nano titanium oxide, nano silicon, nanometer hydroxide
Aluminium, modified glass-fiber, TDE and silane microcapsule-coated ammonium polyphosphate are well mixed, in 1800r/min stirrings
45min, is subsequently added into cumyl peroxide and methyl ethyl ketone peroxide is well mixed, and it is resistance to that ultrasonic disperse 12min obtains high tenacity
The modified unsaturated polyester resin of high temperature.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (9)
1. the resistant to elevated temperatures modified unsaturated polyester resin of a kind of high tenacity, it is characterised in that its raw material includes by weight：Along fourth
25-35 parts of enedioic acid acid anhydride, isophthalic anhydride 2-5 parts, phthalic anhydride 4-8 parts, ethyl acetate 2-5 parts, methacrylic acid
Methyl esters 1-5 parts, benzenetriol 2-6 parts, hydroquinones 3-5 parts, dicyclopentadiene 4-8 parts, 1-4 parts of cobalt naphthenate styrene, phosphoric acid
4-8 parts of ester melamine, methyl ethyl ketone peroxide 3-6 parts, cumyl peroxide 1-4 parts, silane resin acceptor kh-550 2-5 parts,
Nano titanium oxide 3-5 parts, nano silicon 3-6 parts, nano-aluminum hydroxide 2-5 parts, modified glass-fiber 4-8 parts, ten bromines
Diphenylethane 2-5 parts, 2-5 parts of silane microcapsule-coated ammonium polyphosphate, ethylene glycol 5-15 parts, diglycol 3-5 parts, the third two
Alcohol 4-9 parts.
2. the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity according to claim 1, it is characterised in that modified glass
Fiber is prepared by following technique：Tetrabutylammonium iodide and deionized water are well mixed, 65-75 DEG C is then heated to, connect
Addition fiberglass powder and sodium hydroxide solution is well mixed, be then warming up to 75-85 DEG C, be incubated 20-40min, suction filtration is washed
Watery hydrochloric acid regulation pH to 1.5-2.5 is added after washing, then 10-14h is dried in 75-85 DEG C in neutrality to solution after filtering and washing,
It is cooled to room temperature and obtains modified glass-fiber.
3. the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity according to claim 1 and 2, it is characterised in that modified
In the preparation process of glass fibre, the weight ratio of tetrabutylammonium iodide, deionized water, fiberglass powder and sodium hydroxide solution is
1-3：2-4：3-5：4-8.
4. the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity according to claim any one of 1-3, it is characterised in that
Maleic anhydride, isophthalic anhydride, phthalic anhydride, ethyl acetate, methyl methacrylate, benzenetriol, to benzene two
The weight ratio of phenol, dicyclopentadiene and cobalt naphthenate styrene is 28-32：3-4：5-7：3-4：2-4：3-5：3.5-4.5：5-7：
2-3。
5. the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity according to claim any one of 1-4, it is characterised in that
Methyl ethyl ketone peroxide, silane resin acceptor kh-550, nano titanium oxide, nano silicon, nano-aluminum hydroxide and modified glass
The weight ratio of glass fiber is 4-5：3-4：3.5-4.5：4-5：3-4：5-7.
6. the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity according to claim any one of 1-5, it is characterised in that
The weight ratio of nano titanium oxide, TDE and silane microcapsule-coated ammonium polyphosphate is 3.5-4.5：3-4：3-4.
7. the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity according to claim any one of 1-6, it is characterised in that
Its raw material includes by weight：Maleic anhydride 28-32 parts, isophthalic anhydride 3-4 parts, phthalic anhydride 5-7 parts, second
Acetoacetic ester 3-4 parts, methyl methacrylate 2-4 parts, benzenetriol 3-5 parts, hydroquinones 3.5-4.5 parts, dicyclopentadiene 5-7
Part, 2-3 parts of cobalt naphthenate styrene, 5-7 parts of phosphate melamine, methyl ethyl ketone peroxide 4-5 parts, cumyl peroxide 2-
3 parts, silane resin acceptor kh-550 3-4 parts, nano titanium oxide 3.5-4.5 parts, nano silicon 4-5 parts, nanometer hydroxide
Aluminium 3-4 parts, modified glass-fiber 5-7 parts, TDE 3-4 parts, 3-4 parts of silane microcapsule-coated ammonium polyphosphate, second two
Alcohol 8-12 parts, diglycol 3.5-4.5 parts, propane diols 5-8 parts.
8. the resistant to elevated temperatures modified unsaturated polyester resin of high tenacity according to claim any one of 1-7, it is characterised in that
Its raw material includes by weight：30 parts of maleic anhydride, 3.5 parts of isophthalic anhydride, 6 parts of phthalic anhydride, acetic acid second
3.5 parts of ester, 3 parts of methyl methacrylate, 4 parts of benzenetriol, 4 parts of hydroquinones, 6 parts of dicyclopentadiene, cobalt naphthenate styrene
2.5 parts, 6 parts of phosphate melamine, 4.5 parts of methyl ethyl ketone peroxide, 2.5 parts of cumyl peroxide, silane coupler KH-
5503.5 parts, 4 parts of nano titanium oxide, 4.5 parts of nano silicon, 3.5 parts of nano-aluminum hydroxide, 6 parts of modified glass-fiber,
3.5 parts of TDE, 3.5 parts of silane microcapsule-coated ammonium polyphosphate, 10 parts of ethylene glycol, 4 parts of diglycol, the third two
6.5 parts of alcohol.
9. the preparation side of a kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity according to claim any one of 1-8
Method, it is characterised in that comprise the following steps：
S1, ethylene glycol, diglycol, propane diols, phthalic anhydride and isophthalic anhydride are well mixed, be warming up to
180-220 DEG C of insulation 1-3h, is then cooled to 150-160 DEG C, adds maleic anhydride, ethyl acetate and methyl methacrylate
Ester is well mixed, and then heats to 180-190 DEG C, is incubated 2-4h, is cooled to room temperature and obtains material a；
S2, to benzenetriol is added in material a, be warming up to 195-205 DEG C, be incubated 1-3h, it is 0.1-0.2Gpa companies control vacuum
The continuous 1-3h control acid numbers that vacuumize stop vacuumizing and start to be cooled to 175-185 DEG C of input to benzene two after 20-30mgKOH/g
Phenol is well mixed, cold to go to room temperature to obtain material b；
S3, to dicyclopentadiene and cobalt naphthenate styrene is added in material b, be warming up to 125-145 DEG C, be incubated 0.5-1.5h,
Then 30-50min is stirred in 400-600r/min, is then cooled to 60-80 DEG C, be incubated 0.5-1.5h, be subsequently added into phosphate
Melamine, 15-25min is stirred in 250-350r/min, is cooled to room temperature and is obtained material c；
S4, in material c add silane resin acceptor kh-550, nano titanium oxide, nano silicon, nano-aluminum hydroxide,
Modified glass-fiber, TDE and silane microcapsule-coated ammonium polyphosphate are well mixed, and are stirred in 1500-2500r/min
30-50min is mixed, cumyl peroxide is subsequently added into and methyl ethyl ketone peroxide is well mixed, ultrasonic disperse 10-20min is obtained
The resistant to elevated temperatures modified unsaturated polyester resin of high tenacity.
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| CN111748083A (en) * | 2020-06-02 | 2020-10-09 | 山东凯威尔新材料有限公司 | High-toughness polyester resin and synthesis method thereof |
| CN114716801A (en) * | 2022-06-08 | 2022-07-08 | 河南源宏高分子新材料有限公司 | Polyester material with strong toughness and preparation method thereof |
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| CN107916581A (en) * | 2017-10-19 | 2018-04-17 | 无为县荣华鬃刷制品有限公司 | A kind of toughened antiwear dyestuff for pig hair printing and dyeing |
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| CN109206562A (en) * | 2018-11-22 | 2019-01-15 | 安徽汇创新材料有限公司 | A kind of glass toughening manure pit and preparation method thereof |
| CN110903746A (en) * | 2019-05-10 | 2020-03-24 | 扬州润友复合材料有限公司 | Graphene modified unsaturated polyester resin adhesive and preparation method thereof |
| CN111748083A (en) * | 2020-06-02 | 2020-10-09 | 山东凯威尔新材料有限公司 | High-toughness polyester resin and synthesis method thereof |
| CN114716801A (en) * | 2022-06-08 | 2022-07-08 | 河南源宏高分子新材料有限公司 | Polyester material with strong toughness and preparation method thereof |
| CN115028466A (en) * | 2022-06-21 | 2022-09-09 | 上海鼎炘实业有限公司 | Carbon fiber composite material and preparation method thereof |
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