CN107880257A - Flame-retardant material with high refractive index, manufacturing method thereof and flame-retardant polymer with high refractive index - Google Patents
Flame-retardant material with high refractive index, manufacturing method thereof and flame-retardant polymer with high refractive index Download PDFInfo
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- CN107880257A CN107880257A CN201611158567.7A CN201611158567A CN107880257A CN 107880257 A CN107880257 A CN 107880257A CN 201611158567 A CN201611158567 A CN 201611158567A CN 107880257 A CN107880257 A CN 107880257A
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- phenyl ring
- retardant
- fire
- esters
- flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 172
- 229920000642 polymer Polymers 0.000 title claims abstract description 76
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 183
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 150000002148 esters Chemical class 0.000 claims abstract description 48
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 113
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 100
- 238000004079 fireproofing Methods 0.000 claims description 79
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 41
- 229910052698 phosphorus Inorganic materials 0.000 claims description 41
- 239000011574 phosphorus Substances 0.000 claims description 41
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 230000035484 reaction time Effects 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 abstract 2
- 229920006389 polyphenyl polymer Polymers 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002341 toxic gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PRSQQFKBKGHKPP-UHFFFAOYSA-N Cc1cc(-c2ccccc2C2(c3ccc(CCCO)cc3)c(cc3)ccc3OCCO)c2cc1 Chemical compound Cc1cc(-c2ccccc2C2(c3ccc(CCCO)cc3)c(cc3)ccc3OCCO)c2cc1 PRSQQFKBKGHKPP-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for manufacturing a flame-retardant material with high refractive index, which comprises the following steps: polymerizing dicarboxylic acid, alkylene glycol, poly-phenylene glycol and a first poly-phenylene ester flame retardant to form a polymer, wherein the dicarboxylic acid is 50 to 65 parts by weight, the alkylene glycol is 20 to 30 parts by weight, the poly-phenylene glycol is 9 to 15 parts by weight, and the first poly-phenylene ester flame retardant is 1 to 4 parts by weight; and a mixed polymer and a second polyphenyl cyclic ester flame retardant, wherein the second polyphenyl cyclic ester flame retardant is 4-10 parts by weight. The flame retardant material is an environment-friendly halogen-free flame retardant and has the advantages of high refractive index, good flame retardance and good heat resistance.
Description
Technical field
The present invention be on fire proofing and its manufacture method with high index of refraction, it is and fire-retardant poly- with high index of refraction
Compound, hindered especially with regard to dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the polymerization of the esters of phenyl ring more than first fire retardant is made with being formed
Polymer is fired, remixes flame-retardant polymer and the esters of phenyl ring more than second fire retardant to form the manufacture method of fire proofing.
Background technology
Fire retardant is a kind of auxiliary agent for the flame retardancy that can improve combustibles or combustible, and then prevent combustibles and
Combustible is ignited and suppressed the effect of propagation of flame, to ensure that the process in use above-mentioned material can be safer.In crowd
In more fire retardants, because halogenated flame retardant has the advantages of flame retarding efficiency is high, fire resistance is good and cheap, and as most
The based flame retardant being widely employed.However, halogenated flame retardant can generate substantial amounts of smog and tool in thermal cracking or burning
Mordant toxic gas (such as：Hydrogen halide), there is sizable harm for environment.
Based on considering for environmental protection, it should substitute halogenated flame retardant with other types of nontoxic fire retardant, seem the resistance of phosphorus system
Fire agent, Sb system fire retardant, aluminium hydroxide fire retardant or flame retardant of magnesium hydroxide.However, these fire retardants still lack with some
Point, such as：Heat endurance is bad, it is easy hydrolysis occurs or volatility is high, and its application is restricted.In addition, work as these
When in the optical module that fire retardant be used to having fire-retardant demand, there is also because the refractive index of fire retardant is not high and color is partially yellow,
And there is the problem of harmful effect for the transparency, light transmittance and structure design of optical module.
In view of this, it is necessary to which a kind of new fire proofing and its manufacture method are above-mentioned to solve the problems, such as.
The content of the invention
The one of the purpose of the present invention is to provide a kind of new fire proofing and its manufacture method, and it can substantially be solved
The certainly above mentioned problem of prior art.
The present invention provides a kind of manufacture method of the fire proofing with high index of refraction, comprises the steps of：
Make dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the polymerization of the esters of phenyl ring more than first fire retardant to form polymer, its
Middle dicarboxylic acids is 50 to 65 parts by weight, and alkylene glycol is 20 to 30 parts by weight, and more phenyl ring glycol are 9 to 15 parts by weight, and are had
Chemical formula as shown in formula (1)：
The esters of phenyl ring more than first fire retardant is 1 to 4 parts by weight, and with the chemical formula as shown in formula (2)：
Wherein, x is 24 to 30；And
Mixed polymer and the esters fire retardant of phenyl ring more than second, the esters of phenyl ring more than second fire retardant are 4 to 10 parts by weight, and
With the chemical formula as shown in formula (2).
In one embodiment, it is total in dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the esters fire retardant of phenyl ring more than first
Phosphorus content is 1000ppm to 3500ppm.
In one embodiment, the phosphorus content in polymer and the esters fire retardant of phenyl ring more than second is at least 6800ppm.
In one embodiment, dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the esters fire retardant of phenyl ring more than first are made in temperature
Spend to be polymerize at 220 DEG C to 250 DEG C.
In one embodiment, the polymerization of dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the esters fire retardant of phenyl ring more than first
Reaction time is 150 minutes to 200 minutes.
In one embodiment, dicarboxylic acids is terephthalic acid (TPA) (Terephthalic acid, TPA).
In one embodiment, alkylene glycol is ethylene glycol (Ethylene glycol, EG).
The present invention provides a kind of flame-retardant polymer with high index of refraction, has the chemical formula as shown in formula (3)：
Wherein, x is that 24 to 30, m and n is respectively 50 to 200, and p is 1 to 5.
The present invention provides a kind of fire proofing with high index of refraction, comprising：Flame-retardant polymer with high index of refraction；With
And the esters fire retardant of phenyl ring more than one, there is the chemical formula as shown in formula (2)：
Wherein, x is 24 to 30.
In one embodiment, the phosphorus content in the fire proofing with high index of refraction is 6800ppm to 7500ppm.
Compared with prior art, fire proofing of the invention and flame-retardant polymer are environmentally friendly halogen-free flame retardants, therefore
Toxic gas will not be discharged in combustion process, and there is the advantages of high index of refraction, anti-flammability is good and heat-resist, therefore applies phase
When extensive.
Brief description of the drawings
The present invention above and other aspect, feature and further advantage are with reference to description and coordinate accompanying drawing to be become apparent from
Understanding, wherein：
Fig. 1 is the manufacturing process of the fire proofing with high index of refraction depicted according to an embodiment of the present invention
Figure；And
During Fig. 2 is shown in manufacture flame-retardant polymer, in order to which stirring rod is a fixed rotating speed institute in maintenance reaction groove
The experimental result that the voltage that need to be supplied changes with polymerization reaction time；
Wherein, symbol description：
100：Manufacture method
110、120：Operation
210、220：Data point.
Embodiment
Following disclosure provides many different embodiments or example, to realize the different characteristic of the present invention.It is specific
The composition and layout of example are described below, to simplify the present invention.Certainly these are only examples, and are not used to limit.
In order to solve the problems, such as described in prior art, the present invention provides a kind of fire proofing and its manufacture method, this resistance
Contain a kind of flame-retardant polymer in combustible material.The fire proofing and flame-retardant polymer of the present invention is environmentally friendly halogen-free flame retardants, because
This will not discharge toxic gas in combustion, and have the advantages of high index of refraction, anti-flammability is good and heat-resist, therefore should
With quite extensive.For example, due to the advantage with high index of refraction so that this fire proofing and flame-retardant polymer are used for light
When learning in component, optical module thinning can be made.
The method of manufacture fire proofing comprises the steps of：Prepare dicarboxylic acids, alkylene glycol, more phenyl ring glycol and more phenyl ring
Esters fire retardant, first more phenyl ring esters fire retardants of a part and dicarboxylic acids, alkylene glycol and more phenyl ring glycol are copolymerized with shape
Into flame-retardant polymer, add remaining more phenyl ring esters fire retardant and be blended with this flame-retardant polymer, to form fire proofing.
Detailed manufacturing step refers to Fig. 1 and described below.
Fig. 1 illustrates the manufacture method 100 of the fire proofing with high index of refraction, and it includes operation 110 and operation 120.
Operation 110, dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the polymerization of the esters of phenyl ring more than first fire retardant is set to form fire-retardant polymerization
Thing, wherein dicarboxylic acids are 50 to 65 parts by weight, and alkylene glycol is 20 to 30 parts by weight, and more phenyl ring glycol are 9 to 15 parts by weight, the
The esters of phenyl ring more than one fire retardant is 1 to 4 parts by weight.In detail, more phenyl ring glycol have the chemical formula as shown in formula (1)：
Its entitled 9,9- bis--[(4- hydroxy ethoxies) phenyl] fluorenes of chemistry (bisphenoxyethanolfluorene,
BPEF)；The esters of phenyl ring more than first fire retardant has the chemical formula as shown in formula (2)：
Wherein, x is 24 to 30.In one embodiment, the esters of phenyl ring more than first fire retardant can be from Japanese three wide limited public affairs
Department (Sanko Co., Ltd.s) buys, trade name M-Ester Polycondensation (ME-P8).
Because the both ends of dicarboxylic acids have carboxyl (- COOH), alkylene glycol, more phenyl ring glycol and the resistance of the esters of phenyl ring more than first
Combustion agent all has two hydroxyls (- OH), therefore these reactants can carry out esterification and be copolymerized to form flame-retardant polymer.With
Part by weight between dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the esters fire retardant of phenyl ring more than first is different, this fire-retardant polymerization
The part by weight of each monomeric unit also can be different therewith in thing.For example, if dicarboxylic acids, alkylene glycol, more phenyl ring glycol and
The weight ratio of the esters fire retardant of phenyl ring more than first is 1:2:3:4, then by dicarboxylic acids, alkylene glycol, more phenyl ring glycol and more than first
The weight ratio of each monomeric unit in the flame-retardant polymer that phenyl ring esters fire retardant is formed also can be close to 1:2:3:4.
In one embodiment, dicarboxylic acids is terephthalic acid (TPA) (Terephthalic acid, TPA), and alkylene glycol is second
Glycol (Ethylene glycol, EG), therefore, hindered by dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the esters of phenyl ring more than first
The flame-retardant polymer that combustion agent is generated has the chemical formula as shown in formula (3)：
Wherein, x is that 24 to 30, m and n is respectively 50 to 200, and p is 1 to 5.However, formed inflaming retarding copolymer when
Wait, may also be formed simultaneously other by terephthalic acid (TPA), ethylene glycol, more phenyl ring glycol and the esters of phenyl ring more than first fire retardant institute shape
Into copolymer.For example, it is possible to create PET (polyethylene terephthalate,
PET), by terephthalic acid (TPA) and more phenyl ring glycol copolymerization form polymer, by terephthalic acid (TPA) and the esters of phenyl ring more than first hinder
Polymer that combustion agent copolymerization forms etc..
Because more phenyl ring glycol and the esters fire retardant of phenyl ring more than first have benzene ring structure, therefore above-mentioned flame-retardant polymer contains
Benzene ring structure and there is high index of refraction.Specifically for, the esters fire retardant of phenyl ring more than first contains phosphorus (P), is a kind of phosphorous flame-retardant
Agent, its fire-retardant mechanism are as follows：In combustion, scission of link can occur for the C-P bond in the esters fire retardant of phenyl ring more than first, and shape
Into the compound with the chemical formula as shown in formula (4),
Next, this compound can further decompose and form phosphoric acid (phosphoric acid), phosphoric acid dehydration polymerization and
Form metaphosphoric acid (metaphosphoric acid, (HPO3)n), metaphosphoric acid is a kind of polymer of stabilization, and with strong dehydration
Property, the surface that can be covered in combustible or combustibles enters and stopped that internal imflammable gas overflows to completely cut off external oxygen, reaches
Flame retardant effect to fire retardation, therefore fire retardant can be directly proportional to the phosphorus content in fire retardant.Due to phenyl ring esters more than first
Fire retardant is a kind of polymer electrolyte fire retardant, and its thermal cracking temperature is about 362.1 DEG C, therefore is not easy carrying out pet reaction
During thermal cracking occurs.Because heat resistance is more preferable than in general low molecule amount fire retardant, therefore the esters of phenyl ring more than first are fire-retardant
Contained phosphorus can remain in flame-retardant polymer with hardly losing during flame-retardant polymer is formed in agent.Due to fire-retardant
Also there is the structure similar with the esters fire retardant of phenyl ring more than first, therefore, this flame-retardant polymer also can be according to above-mentioned in polymer
Fire-retardant mechanism and disconnect C-P bond, formed metaphosphoric acid to avoid external oxygen from being reacted with combustible or combustibles, and
Stop that the imflammable gas inside combustible or combustibles overflows, and there is good flame retardant effect.In addition, in flame-retardant polymer
Benzene ring structure, in addition to it can make flame-retardant polymer that there is high index of refraction, can also improve flame-retardant polymer into carbon, and
Lift the flame retardant effect of flame-retardant polymer.
However, it is expressly noted that because the esters of phenyl ring more than first fire retardant is a kind of polymer electrolyte fire retardant, thus with
When other reactants are copolymerized, polymerization effect is poor and needs longer polymerization time, therefore, it is necessary to adjust phenyl ring more than first
Ratio between esters fire retardant and other reactants, to reach optimal polymerization effect.In one embodiment, dicarboxylic acids,
Total phosphorus content in alkylene glycol, more phenyl ring glycol and the esters fire retardant of phenyl ring more than first is 1000ppm to 3500ppm, is being adjusted
In the case that whole total phosphorus content is fallen within this section, dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the esters of phenyl ring more than first are fire-retardant
Polymerization effect between agent is good, rapidly can react to form flame-retardant polymer.
The condition of polymerisation can be adjusted with the dosage of reactant.In one embodiment, dicarboxylic acids, alkane are made
Support glycol, more phenyl ring glycol and the esters of phenyl ring more than first fire retardant are, for example, to be polymerize at 220 DEG C to 250 DEG C in temperature, and
Polymerization reaction time is, for example, 150 minutes to 200 minutes.
Next, in operation 120, flame-retardant polymer and the esters fire retardant of phenyl ring more than second are mixed to form fire proofing,
Phenyl ring esters fire retardant is 4 to 10 parts by weight wherein more than second, and equally has the chemical formula as shown in formula (2).In operation 120
In, the esters of phenyl ring more than second fire retardant can't be chemically reacted with flame-retardant polymer, and both are deposited with the kenel of mixture for this
.As it was previously stated, the esters of phenyl ring more than second fire retardant has good anti-flammability in itself, therefore, can by operation 120
Increase the phosphorus content of the fire proofing of the present invention, and reach the effect of lifting anti-flammability.
In summary, the method for present invention manufacture fire proofing includes two operations.In operation 110, first add
More phenyl ring esters fire retardants are copolymerized with dicarboxylic acids, alkylene glycol and more phenyl ring glycol, in this step, adjust above-mentioned reaction
Part by weight between thing, this copolyreaction is set to form more polymer within the shorter reaction time.Next,
In operation 120, more phenyl ring esters fire retardants that anti-flammability can be lifted by adding other are blended with polymer, and the present invention is logical
The mode for crossing the above-mentioned more phenyl ring esters fire retardants of two benches addition forms fire proofing, overcomes more phenyl ring esters of polymer electrolyte
Based flame retardant needs the problem of longer polymerization reaction time.
Property analysis are carried out finally, for this fire proofing, when the phosphorus content in this fire proofing is at least 6800ppm
When, this resistance is evaluated according to the plastic cement flammability standards UL94 issued by Underwriters Laboratories companies of the U.S.
The anti-flammability of combustible material, the anti-flammability of this fire proofing is up to quite excellent V0 grades.V0 grades are represented in vertical combustion
In the case of, sample can stop burning in 10 seconds, and allow along with the incombustible particle that drips.In general, V0 grades
Fire proofing can provide quite good flame retardant effect for product.Therefore, dicarboxylic acids, alkylene glycol, more phenyl ring glycol, first
The flame retardant effect that reaches needed for the dosage of more phenyl ring esters fire retardants and the esters fire retardant of phenyl ring more than second is visual final and carry out
Adjustment, the phosphorus content in fire proofing are not restricted at least 6800ppm, and the phosphorus content in fire proofing is higher, anti-flammability
It is better.In the case where considering cost, there is the phosphorus content in the fire proofing of high index of refraction can be for example 6800ppm extremely
7500ppm。
The refractive index of general commercially available optics plastic cement is about 1.4 to 1.6.For example, polymethyl methacrylate
The refractive index of (Polymethylmethacrylate, PMMA) is about 1.49；PET (polyethylene
Terephthalate, PET) refractive index be about 1.56 to 1.57.However, the refractive index of the fire proofing of the present invention may be up to
1.65, exceed the refractive index of general commercially available optics plastic cement, therefore the fire proofing of the present invention is applied to manufacture optical module.When making
With refractive index higher material manufacture optical module when (such as：Optical lens module, plastic cement camera lens, optical film or optics are fine
Dimension), these optical modules can be enable to be designed to be more frivolous, therefore the fire proofing of the present invention not only conforms to market and needed
Ask, application is also more extensive.
Following embodiment is that the particular aspect of the present invention is described in detail, and makes to have in the technical field of the invention and lead to
Normal skill is carried out the present invention.Following embodiment is not applied to limit the present invention.
Experimental example 1：Observe the reaction that terephthalic acid (TPA), ethylene glycol and more phenyl ring esters fire retardants form flame-retardant polymer
Journey
This experimental example is to utilize terephthalic acid (TPA) (Terephthalic acid, TPA), ethylene glycol (Ethylene
Glycol, EG) and more phenyl ring esters fire retardants as reactant, more phenyl ring esters fire retardants can be from the wide Co., Ltd's purchase of Japan three
, trade name M-Ester Polycondensation (ME-P8).Observe above-mentioned reactant and form the anti-of flame-retardant polymer
Answer process.In this experimental example, more phenyl ring glycol are not added in reactant, because the molecular weight of more phenyl ring glycol
It is more much smaller than more phenyl ring esters fire retardants, therefore whether there is more phenyl ring glycol in reactant, it is fire-retardant for what is be ultimately formed
The influence of the molecular weight of polymer is simultaneously little.Therefore, can be fire-retardant with terephthalic acid (TPA), ethylene glycol and more phenyl ring esters by observing
Agent as reactant to form the course of reaction of flame-retardant polymer, come deduce with terephthalic acid (TPA), ethylene glycol, more phenyl ring glycol and
More phenyl ring esters fire retardants are as reactant to form the course of reaction of flame-retardant polymer.
In this experimental example, observing two kinds has the reaction of reactant formation flame-retardant polymer of different total phosphorus contents
Journey, embodiment one and embodiment two represent two kinds of different manufacture methods, and in embodiment one, reactant used is included to benzene
Dioctyl phthalate, ethylene glycol and ME-P8, total phosphorus content 7000ppm.In embodiment two, reactant used includes terephthaldehyde
Acid, ethylene glycol and ME-P8, total phosphorus content 3500ppm.The reactant of embodiment one and embodiment two is placed in reactive tank respectively
In, polymerisation is carried out to form flame-retardant polymer.
Fig. 2 is refer to, during Fig. 2 is shown in manufacture flame-retardant polymer, in order to which stirring rod is one in maintenance reaction groove
The experimental result that the voltage of supply needed for fixed rotating speed changes with polymerization reaction time, transverse axis represent polymerization reaction time and (divided
Clock), the longitudinal axis represent in order in maintenance reaction groove stirring rod as the voltage (kV) supplied needed for a fixed rotating speed.In terephthaldehyde
, it is necessary to mix above-mentioned reactant using stirring rod during acid, ethylene glycol and more phenyl ring esters fire retardants progress polymerisation
Close uniformly, with the increase of polymerization reaction time, the polymer generated is also more.Because the molecular weight of polymer is higher, meeting
So that the mixture viscosity in reactive tank rises, therefore the growing amount for working as polymer is more, must just supply higher voltage
There is provided bigger torsion makes its rotating speed maintain to fix to rotate stirring rod.Therefore, reactive tank can be deduced by the height of magnitude of voltage
The number of middle polymer, judge the performance level of polymerisation.It can be deduced by Fig. 2 and be reacted during flame-retardant polymer is manufactured
The experimental result that the growing amount of the polymer formed in groove changes with polymerization reaction time, voltage is higher, represents in reactive tank
The growing amount of polymer is more, and voltage is lower, and the growing amount for representing polymer in reactive tank is fewer.
Fig. 2 is refer to, data point 210 is to carry out polymerizeing measured data point, data point with the reactant of embodiment one
220 is carry out polymerizeing measured data point with the reactant of embodiment two, as can be seen from Figure 2, in data point 210 and data point
In 220, with the increase of polymerization reaction time, voltage is consequently increased, and represents and flame-retardant polymer is increasingly generated in reactive tank.It is special
Not it is noted that among identical polymerization reaction time, embodiment two can be generated than the more fire-retardant polymerization of embodiment one
Thing.For example, when polymerization reaction time is about 180 minutes, the voltage of data point 210 is about 195kV, data point 220
Voltage is about 260kV.It may thus be appreciated that adjustment reactant total phosphorus content in the case of 3500ppm, terephthalic acid (TPA), second two
The efficiency that alcohol and more phenyl ring esters fire retardants are converted to flame-retardant polymer is quite good.Embodiment one is reviewed, due to the addition of
More more phenyl ring esters fire retardants, thus when reacted between be more than 150 minutes after, need longer polymerization reaction time can on the contrary
Form flame-retardant polymer.
Next, when polymerization reaction time is about 180 minutes, property survey is carried out for the fire proofing in reactive tank
Try, the flame-retardant polymer of generation is included in this fire proofing, may also include some still unreacted reactants.Specifically,
For the fire proofing that is formed by embodiment one and embodiment two carry out inherent viscosity (Intrinsic viscosity),
Glass transition temperature (Glass transition temperature, Tg), fusing point (melting temperature, Tm) and
The test of acid value, as a result as shown in Table 1：
Table one
| Embodiment one | Embodiment two | |
| Phosphorus content (ppm) | 7000 | 3500 |
| Inherent viscosity | 0.428 | 0.620 |
| Tg(℃) | 70.0 | 71.0 |
| Tm(℃) | 239.7 | 240.1 |
| Acid value (μ eq/g) | 98 | 30 |
In general, when containing the compound of more HMWs in fire proofing, inherent viscosity is generally also bigger, because
This can judge the number of flame-retardant polymer contained in fire proofing by inherent viscosity numerical value listed in table one.From table one
From the point of view of, the inherent viscosity of the fire proofing formed by embodiment one is less than the fire proofing formed by embodiment two,
This, which is represented in the fire proofing formed by embodiment two, contains more flame-retardant polymer.Also, the characteristic of embodiment two
Viscosity is higher than 0.5 and fusing point is 240.1 DEG C, and this represents this fire proofing and has met demand on general industry, available for making
Make in general optical module.In addition, the acid value of the fire proofing formed by embodiment one, which is higher than, passes through two shapes of embodiment
Into fire proofing, this, which is represented in the fire proofing formed by embodiment one, contains more unreacted terephthalic acid (TPA).
Conversely, the acid value of the fire proofing formed by embodiment two is 30 μ eq/g, then mean the terephthalic acid (TPA) in reactant
Almost reaction finishes completely.Therefore, gathered if this experimental example demonstrates from the reactant for being about 3500ppm with phosphorus content
Close, can make reactant be converted to flame-retardant polymer efficiency it is preferable.
Experimental example 2：Property survey is carried out for the fire proofing for polymerizeing generation by the reactant with different total phosphorus contents
Examination
In this experimental example, the other two kinds reactants with different total phosphorus contents are polymerize with the fire proofing point of generation
Not carry out property test, wherein embodiment three and example IV use two kinds of different manufacture methods respectively.In embodiment three,
Reactant used includes terephthalic acid (TPA) (TPA), ethylene glycol (EG) and ME-P8, total phosphorus content 3500ppm；In embodiment
In four, reactant used includes terephthalic acid (TPA), ethylene glycol and ME-P8, total phosphorus content 4500ppm.Respectively by embodiment
Three and the reactant of example IV be placed in reactive tank, polymerisation is carried out to form fire proofing, except bag in fire proofing
Outside flame-retardant polymer, some still unreacted reactants may be also included.Next, carried out for above-mentioned fire proofing
The test of inherent viscosity, glass transition temperature (Tg), fusing point (Tm) and acid value, as a result as shown in Table 2：
Table two
| Embodiment three | Example IV | |
| TPA (wt%) | 66.10 | 65.23 |
| EG (wt%) | 29.62 | 29.06 |
| ME-P8 (wt%) | 4.28 | 5.71 |
| Phosphorus content (ppm) | 3500 | 4500 |
| Inherent viscosity | 0.618 | 0.413 |
| Tg(℃) | 71.0 | 70.0 |
| Tm(℃) | 240.5 | 239.8 |
| Acid value (μ eq/g) | 32 | 95 |
From the point of view of table two, the inherent viscosity of the fire proofing formed by example IV, which is less than, passes through three shapes of embodiment
Into fire proofing, this, which is represented in the fire proofing formed by embodiment three, contains more flame-retardant polymer, also, its
Inherent viscosity is higher than 0.5 and fusing point is 240.5 DEG C, and this represents this fire proofing and has met demand on general industry, can use
In manufacture in general optical module.In addition, the acid value of the fire proofing formed by example IV, which is higher than, passes through embodiment three
The fire proofing formed, this, which is represented in the fire proofing formed by example IV, contains more unreacted terephthaldehyde
Acid, and the acid value of the fire proofing formed by embodiment three is 32 μ eq/g, then means the terephthalic acid (TPA) in reactant
Almost reaction finishes completely.
It is worth noting that, the total phosphorus content of example IV is only slightly higher than embodiment three, result in example IV to benzene
Polymerization effect between dioctyl phthalate, ethylene glycol and more phenyl ring esters fire retardants is poor, and promotes the resistance formed by example IV
The inherent viscosity of combustible material is smaller and acid value is higher.This experimental example again demonstrates the total phosphorus content in reactant in 3500ppm
In the case of, can make terephthalic acid (TPA), ethylene glycol and more phenyl ring esters fire retardants be converted to the efficiency of flame-retardant polymer compared with
It is good.
Experimental example 3：Property survey is carried out for the fire proofing for polymerizeing generation by differential responses thing and different manufacture methods
Examination
In this experimental example, the fire proofing progress property test of generation is polymerize to the reactant of six kinds of different components,
Wherein comparative example one to four and embodiment five to six use six kinds of different manufacture methods, and the various compositions of fire proofing respectively
And test result is listed in table three.Specifically, the reaction process of comparative example one to comparative example four is all that reactant is all mixed
Esterification is carried out after closing uniformly, forms fire proofing (may including some unreacted reactants), wherein comparative example two
And three fire retardant addition manner is all disposable addition.In addition, included respectively in the reactant of comparative example two and comparative example three
Tradition conventional phosphorus flame retardant CEPPA and DOPO-IT, in esterification process, the fire retardant of part may be in course of reaction
Middle consume, and the phosphorus content for the product (fire proofing) for be ultimately formed declines.Comparative example one to comparative example four reaction
The test of the property of thing composition and fire proofing refer to table three.
In embodiment five, reactant used includes terephthalic acid (TPA), ethylene glycol and fire retardant ME-P8, wherein total phosphorus
Content is 7000ppm.The step of esterification of embodiment 5 is as follows：Mix the fire retardant of terephthalic acid (TPA), ethylene glycol and part
ME-P8, total phosphorus content 3500ppm, it polymerize above-mentioned reactant to form flame-retardant polymer；Next, mix this fire-retardant polymerization
Thing and remaining more phenyl ring esters fire retardant, form final fire proofing.It is worth noting that, the fire retardant of embodiment five adds
Add mode is secondary addition.During the course of the reaction, more phenyl ring esters fire retardants of part may consume during the course of the reaction, and
So that the phosphorus content for the product (fire proofing) being ultimately formed declines.The reactant composition of embodiment five and the property of fire proofing
Matter test refer to table three.
In embodiment six, reactant used includes terephthalic acid (TPA), ethylene glycol, more phenyl ring glycol and fire retardant ME-
P8, wherein reactant total phosphorus content are 7000ppm.The step of esterification of embodiment six is as follows：Mix terephthalic acid (TPA), second
The fire retardant ME-P8 of glycol, more phenyl ring glycol and part, total phosphorus content 3500ppm, it is fire-retardant to be formed to polymerize above-mentioned reactant
Polymer；Next, mixing this flame-retardant polymer and remaining more phenyl ring esters fire retardant, final fire proofing is formed.Value
Obtain it is noted that the fire retardant addition manner of embodiment six is also secondary addition.The reactant composition and fire-retardant material of embodiment six
The property test of material refer to table three.
Table three
From the point of view of table three, the refractive index of the fire proofing of embodiment six is up to 1.6596, the conventional high refraction than industrially
Rate material (such as：Polymethyl methacrylate and PET) refractive index it is higher.Also, can according to plastic cement
Combustion property standard UL94 evaluates the anti-flammability of this fire proofing, and the anti-flammability of the fire proofing of embodiment six is quite excellent V0
Grade.In addition, the inherent viscosity of this fire proofing is higher than 0.5, fusing point is 220.7 DEG C.Thus, it can be known that in all embodiments and
In comparative example, fire proofing of the invention has highest refractive index and most excellent anti-flammability, and inherent viscosity and fusing point
Also the demand of general manufacture optical module can be reached.
In addition, from the point of view of the experimental data of comparative example two, comparative example three and embodiment five, in embodiment five, reactant
Phosphorus content 7000ppm, the phosphorus content of product is 6910ppm, phosphorus loss is less than comparative example two and comparative example three, it was demonstrated that choosing
The phosphorus in esterification reaction process can be reduced really as reactant with the fire retardant ME-P8 of the preferable polymer electrolyte of heat resistance
Loss so that the fire proofing being ultimately formed has preferable anti-flammability.
In summary, the present invention first makes some more phenyl ring esters by way of two benches add more phenyl ring esters fire retardants
Based flame retardant forms the flame-retardant polymer with high index of refraction with dicarboxylic acids, alkylene glycol and more phenyl ring glycol, further adds
Add the more phenyl ring esters fire retardants that can lift anti-flammability to be blended with flame-retardant polymer, overcome more phenyl ring of polymer electrolyte
Esters fire retardant needs the problem of longer polymerization reaction time, while obtains good and heat-resist with high index of refraction, anti-flammability
Fire proofing.Also, the fire proofing and flame-retardant polymer due to the present invention are free of halogen, therefore in combustion will not
As halogenated flame retardant generally generates substantial amounts of smog and has corrosive toxic gas, and it is more environmentally friendly.Based on above-mentioned more
The application of kind advantage, fire proofing of the invention and flame-retardant polymer is than general traditional high-index material and fire proofing
It is more extensive.
Although the present invention is disclosed above with embodiment, other embodiment is also possible to.Therefore, claims are asked
Spirit and scope be not limited to narration contained by embodiment herein.
It is any to be familiar with this those skilled in the art and understand, without departing from the spirit and scope of the present invention, when various changes can be made
With retouching, therefore protection scope of the present invention depending on appended claims institute defender when being defined.
Claims (10)
1. a kind of manufacture method of the fire proofing with high index of refraction, it is characterised in that include：
Make dicarboxylic acids, alkylene glycol, more phenyl ring glycol and the polymerization of the esters of phenyl ring more than first fire retardant to form polymer, wherein institute
It is 50 to 65 parts by weight to state dicarboxylic acids, and the alkylene glycol is 20 to 30 parts by weight, and more phenyl ring glycol are 9 to 15 weight
Part, and with the chemical formula as shown in formula (1)：
The esters of phenyl ring more than first fire retardant is 1 to 4 parts by weight, and with the chemical formula as shown in formula (2)：
Wherein, x is 24 to 30；And
The polymer and the esters fire retardant of phenyl ring more than second are mixed, the esters of phenyl ring more than second fire retardant is 4 to 10 weight
Part, and with the chemical formula as shown in formula (2).
2. manufacture method according to claim 1, wherein the dicarboxylic acids, the alkylene glycol, more phenyl ring glycol
And the total phosphorus content in the esters fire retardant of phenyl ring more than first is 1000ppm to 3500ppm.
3. manufacture method according to claim 1, wherein in the polymer and the esters fire retardant of phenyl ring more than second
Phosphorus content be at least 6800ppm.
4. manufacture method according to claim 1, wherein making the dicarboxylic acids, the alkylene glycol, more phenyl ring two
Alcohol and the esters of phenyl ring more than first fire retardant are polymerize at being 220 DEG C to 250 DEG C in temperature.
5. manufacture method according to claim 1, wherein the dicarboxylic acids, the alkylene glycol, more phenyl ring glycol
And the polymerization reaction time of the esters fire retardant of phenyl ring more than first is 150 minutes to 200 minutes.
6. manufacture method according to claim 1, wherein the dicarboxylic acids is terephthalic acid (TPA).
7. manufacture method according to claim 1, wherein the alkylene glycol is ethylene glycol.
8. a kind of flame-retardant polymer with high index of refraction, it is characterised in that there is the chemical formula as shown in formula (3)：
Wherein, x is that 24 to 30, m and n is respectively 50 to 200, and p is 1 to 5.
9. a kind of fire proofing with high index of refraction, it is characterised in that include：
Flame-retardant polymer according to claim 8 with high index of refraction；And
More phenyl ring esters fire retardants, there is the chemical formula as shown in formula (2)：
Wherein, x is 24 to 30.
10. fire proofing according to claim 9, wherein phosphorus content are 6800ppm to 7500ppm.
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| CN102617828A (en) * | 2011-02-01 | 2012-08-01 | 财团法人工业技术研究院 | High refractive index polymer, optical element and photoelectric device comprising the same |
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| CN102617828A (en) * | 2011-02-01 | 2012-08-01 | 财团法人工业技术研究院 | High refractive index polymer, optical element and photoelectric device comprising the same |
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