CN106947070A - Fire-retardant polyester - Google Patents
Fire-retardant polyester Download PDFInfo
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- CN106947070A CN106947070A CN201710041782.7A CN201710041782A CN106947070A CN 106947070 A CN106947070 A CN 106947070A CN 201710041782 A CN201710041782 A CN 201710041782A CN 106947070 A CN106947070 A CN 106947070A
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- acid
- fire
- retardant polyester
- anhydride
- monomer
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- 0 C[*+][C@]1OC1ON Chemical compound C[*+][C@]1OC1ON 0.000 description 2
- YPIGGYHFMKJNKV-UHFFFAOYSA-N CCNCC(O)=O Chemical compound CCNCC(O)=O YPIGGYHFMKJNKV-UHFFFAOYSA-N 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G63/68—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
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Abstract
The present invention is that, on a kind of fire-retardant polyester, it has Formulas I structure：
Description
The application is the applying date：On January 16th, 2015, application number：201510022869.0, denomination of invention：Flame retardance poly
The divisional application of ester.
Technical field
The present invention is on a kind of non-halogen reacting fire-retardant polyester, especially with respect to a kind of modified phosphorous unsaturation
Polyester.
Background technology
Known flame retardant is roughly divided into halogenated flame retardant, silicon-series five-retardant and phosphorus flame retardant, wherein halogenated flame retardant certainly
Critical role is captured always from 20th century, because this kind of anti-flammability is good, consumption is few, the performance impact to material is small, and price
It is moderate.However, because halogen can derive problem of environmental pollution, along with the fire-retardant macromolecular material of halogen system in hot tearing and burning
The substantial amounts of flue dust of Shi Shengcheng and corrosive gas, the prospect to halogenated flame retardant have coverd with one layer of shade, increasing user
Particularly electronic/electrical gas industry holds scrupulous attitude to halogenated flame retardant.In recent years, phosphorus flame retardant is because of its low cigarette, nontoxic, low halogen
Or the advantages of Halogen, therefore phosphorus flame retardant has gradually replaced halogenated flame retardant to turn into pair for endeavouring research and development in industry at present
As.
CompoundAnd its derivative is a kind of New Phosphorus developed rapidly the nearly more than ten years (DOPO)
Flame retardant.Due to the special construction of molecule, make it not only than typically cyclic organophosphorus ester heat endurance and chemistry be not steady
It is qualitative good, also have the advantages that phosphorus content height, Halogen, low cigarette, it is nontoxic, do not migrate and fire-retardant lasting.For example, United States Patent (USP)
Publication number the 2009/0198011st and Chinese patent 101525420B are disclosed containing the miscellaneous -10- of 9,10- dihydro-9-oxies
Phospho hetero phenanthrene -10- oxides (9,10-dihydro-9-oxa-10-phosphaphena nthrene-10-oxide, DOPO) into
The fire retardant divided.
However, material (such as ethene system of the above-mentioned fire retardant containing DOPO compositions and non-polar solven or radiation-hardenable
Material)/monomer (such as styrene) compatibility it is not good, in practical application there is compatibility (such as applied to coating) asks
Topic, is easily caused the problems such as coating skewness is separated out with fire proofing after such as solidification, causes it to be limited using scope.
In consideration of it, present invention offer is a kind of to synthesize the convenient modified phosphorous unsaturated polyester (UP) of easy and volume production, have
The group of radiation-curable, and can be with radiation curable material (such as ethene based material)/monomer (such as styrene) phase well
Hold and the mutual cross-linked polymeric of energy；Further, since also having good between the modified phosphorous unsaturated polyester (UP) and non-polar solven
Compatibility, and film forming shrinkage can be further reduced, therefore the scope of application of the fire-retardant polyester is more extensive.
The content of the invention
An object of the present invention is to provide a kind of fire-retardant polyester, and it has Formulas I structure：
Wherein each A' stands alone as residue of dihydric alcohol, and each B' and each B " may be the same or different and stand alone as saturation or not
The residue of saturation acid anhydrides or acid, C' and C " may be the same or different and each stand alone as hydrogen, epoxy acrylate based compound
The residue of residue or the siliceous compound of epoxy radicals, restrictive condition is that C' and C " non-concurrent is hydrogen, and wherein a is 1 to 30 integer, and b is 1
To 30 integer, c is 1 to 15 integer, and wherein the fire-retardant polyester has 20 to 40 acid value.
Another object of the present invention is to provide a kind of coating composition, comprising：Above-mentioned fire-retardant polyester, vinyl monomer
And polymerization initiator.
It is still another object of the present invention to provide a kind of method for preparing fire-retardant polyester, it comprises the following steps：
(a) by least one dihydric alcohol, at least one saturation or unsaturated acid anhydride or acid andProgress polymerize instead
Should；
(b) further at least one saturation or unsaturated acid anhydride or acid and the product of step (a) are reacted；
(c) product of epoxy acrylate based compound or the siliceous compound of epoxy radicals and step (b) is modified instead
Should；And
(d) after step (c) reaction terminates, optionally the siliceous compound of epoxy radicals is added, reaction is modified.
The beneficial effects of the invention are as follows:
1) fire-retardant polyester of the present invention carries out polymerisation using monomer D, obtains higher phosphorus content and stably fire-retardant
Performance.
2) so that acrylate based compound is modified and obtains fire-retardant polyester of the present invention, above-mentioned unsaturated polyester (UP) is in master
There is unsaturated bond (C=C), with radiation-hardenable characteristic on chain.It is simultaneous except providing good component (with monomer or solvent)
Capacitive, is more avoided that the generation of migration and will not separate out, make purposes in practical application more extensive.
3) fire-retardant polyester of the present invention also can be siliceous, and more increases anti-flammability by the flame retardant synergistic effect of phosphorus and silicon
Can, and increase and the adherence of base material.
For above-mentioned purpose, technical characteristic and the advantage of the present invention can be become apparent, the present invention is further described below
Embodiment.
Embodiment
The part embodiment according to the present invention will be specifically described below；Only, in the spirit without departing substantially from the present invention
Under, the present invention still embodiment in many different forms is put into practice, and should not be considered limited to the scope of the present invention
Bright book institute representor.In addition, unless Wen Zhongyou illustrates in addition, in this manual (especially in the protection model of claims
In enclosing) used in " one ", "the" and similar term be interpreted as including odd number and plural form.
Fire-retardant polyester of the present invention be pass through using dihydric alcohol, unsaturated acid anhydride and/or unsaturated acids, saturation acid anhydrides and/
Or saturated acid with(miscellaneous -10- phospho hetero phenanthrenes -10- the oxidations of 10- (2,5- dicarboxypropyls) -9,10- dihydro-9-oxies
Thing, monomer (D)) polymerisation is carried out, and be modified and obtained with acrylate based compound and/or the siliceous compound of epoxy radicals
.Fire-retardant polyester of the present invention is a kind of modified phosphorous unsaturated polyester (UP), and it has unsaturated key (C=C) on main chain,
(that is, cross-linked polymeric can be carried out with radiation-hardenable characteristic under such as ultraviolet light, visible ray or high-energy ray effect and form solid
State product), cross-linking and curing reaction that can be good with other radiation curable material rows, and the fire-retardant polyester of gained with it is conventional
Dilution monomer (such as styrene) or non-polar solven have good compatibility, and purposes is more extensive in practical application.Enter one
Step ground, fire-retardant polyester of the present invention can further include " silicon ", therefore can pass through phosphorus and silicon flame retardant synergistic effect and more gain material
Fire resistance, while the adherence of base material (such as glass baseplate) with being applied can be increased.
According to the compound of formula I of the present invention, a is 1 to 30 integer, and preferably 1 to 8 integer, b is 1 to 30 integer,
Preferably 1 to 8 integer, and c is 1 to 15 integer, preferably 1 to 8 integer, more preferably 1 to 4 integer.If a, b and c
Value it is too high, i.e., molecular weight is excessive, then may in subsequent applications (as be applied to coating) derivation operation problem, for example cause to glue
Spend height.Therefore it is general still regarding selected a, b and c value of actually used need.
Dihydric alcohol of the present invention can be any glycol monomer, and its species has no specifically limited.For example, binary
Alcohol (monomer (A)) may be selected from by ethylene glycol, diethylene glycol, propane diols, DPG, neopentyl glycol, polyethylene glycol, styrene two
Alcohol, hexylene glycol, butanediol, 1- phenyl -1,2- ethylene glycol, the bromo- 2- nitros -1,3- propane diols of 2-, 2- methyl -
2- nitro -1,3- propane diols, double methylol diethyl malonates, hydroquinones and 3,6- dithia -1,8- ethohexadiols
And combinations thereof the group that is constituted.In some embodiments of the present invention, monomer (A) is ethylene glycol, diethylene glycol
(diethylene glycol), propane diols (propylene glycol) or its mixture.A' is as residual obtained by monomer (A)
Base (residue), with monomer (A) for ethylene glycol (HO-CH2CH2- OH) exemplified by, residue A ' it is-CH2CH2-。
Saturation of the present invention or unsaturated acid anhydride or acid are unsaturated acid anhydride or acid and saturation acid anhydrides or sour general name.
Saturation acid anhydrides of the present invention or acid are any saturation acid anhydrides or acid monomers for forming divalent group, and it is special that its species has no
Limitation.For example, the saturation acid anhydrides or acid (monomer (B1)) are selected from by phenylsuccinic acid, benzyl malonic acid, 3- phenyl penta
Diacid, 1,4- diethylamino phenyls acid, 1,2- diethylamino phenyls acid, oxalic acid, malonic acid, succinic acid, equal benzene tertacarbonic acid's dianhydride, 3,3',
4,4'- benzophenone-tetracarboxylic dianhydride, naphthalene dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid acid anhydride, cyclobutanetetracarboxylic dianhydride, 2,3- anthracenes
Dicarboxylic anhydride, 3,4,9,10- tetracarboxylic anhydrides, 1,2,3,4- butane tetracarboxylics acid dianhydride, the tetracarboxylic dianhydride of 1,2,3,4- rings penta, phenyl
Glutaric anhydride, adipic anhydride, 3,3- dimethylated pentanedioic acids acid anhydride, phenylsuccinic acid acid anhydride, hexahydrophthalic anhydride and under tool
Formula structure:
And combinations thereof the group that is constituted, wherein R1
And R2Each stand alone as H or the C1 that is substituted or is unsubstituted is to C15 alkyl., should in some embodiments of the present invention
Saturation acid anhydrides or acid can beOr foregoing combination.
Unsaturated acid anhydride of the present invention or acid are any unsaturated acid anhydride or acid monomers for forming divalent group, its
Species has no specifically limited.For example, the unsaturated acid anhydride or acid (monomer (B2)) be selected from byAnd combinations thereof the group that is constituted, wherein R1And R2Each stand alone as H or be substituted
Or the C1 being unsubstituted is to C15 alkyl.In some embodiments of the present invention, the unsaturated acid anhydride or acid can be maleic acid
(i.e.), fumaric acid (i.e.), maleic anhydride (i.e.) or foregoing combination.
Each B' and each B " may be the same or different and be respectively obtained by monomer (B1) or monomer (B2) in formula I
Residue, be with monomer (B1)Exemplified by, residue isIt is with monomer (B2)Exemplified by, residue is-CH=
CH-, each above-mentioned B' can be same to each other or different to each other and each B " can be same to each other or different to each other, and B' and B " also may be the same or different,
Depending on user's demand.In general, derived from the fire retardant obtained by monomer (B1), can have preferable machine applied to coating
Tool intensity, heat resistance is good but easily occurs xanthochromia, derived from the fire retardant obtained by monomer (B2), and paint solidification speed is fast but easily hard
It is crisp.In addition, residue B ' or residue B " side chain do not have active group, such as H preferably2C=CH- groups, to avoid because of this
The presence of active group and influence the modification result (such as producing other accessory substances being not intended to) of unsaturated polyester (UP).
In some embodiments of the present invention, each B' is as the residue obtained by monomer (B1) or monomer (B2), example
Such asEach B " is preferably as the residue obtained by monomer (B2), for example
In formula I C' and C " may be the same or different and each stand alone as hydrogen, epoxy acrylate based compound
The residue of the residue or the siliceous compound of epoxy radicals (that is, monomer (C2)) of (that is, monomer (C1)), but C' and C " will not be hydrogen simultaneously.
It is with monomer (C1)Exemplified by, C' or C " are as the residue obtained by monomer (C1)With list
Body (C2) isExemplified by, C' or C " are as the residue obtained by monomer (C2)
Above-mentioned monomer (C1) can be (methyl) glycidyl acrylate, 3,4- epoxycyclohexyl-methyls (methyl) acrylic acid
Ester (3,4-epoxycyclohexylmethyl (methyl) acrylate) orOr its combination, wherein R3For H or methyl, and R4To be unsubstituted or through C1
To C15 alkyl, aryl, ester group, sulfonyl, NCO, silylation, siloxy group or acrylate-based substituted divalence
Group.According to the preferred embodiment of the present invention, R4Straight or branched alkylidene for C1 to C15 or selected from following group
Group： AndWherein n is 1 to 15 integer, and m is 1 to 10 integer, and R is H or methyl, and T is In some embodiments of the present invention, monomer (C1) is metering system
Acid glycidyl ester, i.e.,Or 3,4- epoxycyclohexyl-methyl (methyl) acrylate, i.e.,
The above-mentioned siliceous compound monomer (C2) of epoxy radicals is, for example,
Or its combination, R5And R6Each stand alone as C1 to C15 straight or branched alkyl, C1 to C15 straight or branched alkoxyl orR7For C1 to C15 straight or branched alkyl, C1 to C15 straight or branched alkoxyl orR8For C1 to C15 straight or branched alkylidene, polyether-based or arlydene.Preferably
Ground, the monomer (C2) is Or aforementioned combinatorial.In this hair
In bright some embodiments, monomer (C2) is(γ-(metering system
Acyl-oxygen) propyl trimethoxy silicane, 3-Glycidoxypropyltrimethoxysilane) or(2- (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane, 2- (3,4-
Epoxycyclohexyl)ethyltriethoxysilane)。
The fire retardant of the base containing DOPO of current market because the fire retardant of the base containing DOPO is free of active group, therefore with non-pole
Property solvent or radiation-hardenable material (such as ethene based material)/monomer (such as styrene) compatibility it is not good, cause solidification
The problems such as coating skewness or fire proofing are separated out afterwards, the present invention utilizes epoxy acrylate based compound (that is, monomer
(C1)) polyester for having formula III structure is modified,
Wherein residue A ', residue B ' and residue B ", and polymerized unit number a, b, c are as previously described.It is characterized in that the list
Body (C1) active functional group, such as epoxy radicals, active functional group can produce chemical bond with the acid functional group of polyester end
Tie (chemical bonding), the polyester of formula III structure is changed into response type polyester, it is anti-that response type polyester may participate in polymerization
Should, embedded polymer molecular structure, it is to avoid migration, so have the advantages that compatibility is good when applying to coating, and after hardening
Fire retardant is evenly distributed, and will not separate out.
The fire-retardant polyester of present invention tool formula III structure is modified with monomer (C1), makes it have reactive functional group,
Acid functional group's (carboxyl) may be for example remained in vinyl, modifying process, its can optionally with the siliceous compound of an epoxy radicals (i.e.,
Monomer (C2)) reaction is modified, to generate the unsaturated polyester (UP) containing silicon and phosphorus simultaneously, so that through the fire-retardant association of silicon and phosphorus
The fire resistance of same-action (synergy), further lifting material.Apply to through the modified fire retardant of the siliceous compound of epoxy radicals
Coating, presence and base material that can be because of silica functional group have preferably adherence.In the preferred embodiment of the present invention, at least
One C' or C " isAnother C' or C " be selected from by H,
The group constituted.
The ratio of the molal quantity of the siliceous compound of epoxy radicals used (C2) and the molal quantity of polymerized monomer (C1), preferably 1：99
To 1：5.According to the present invention part preferred embodiment in, aforementioned proportion scope, such as, but not limited to 1:99 to 1：90、1:80
To 1：65 and 1:45 to 1：15.The selection of its ratio is determined according to the alkoxy quantity of the siliceous compound of epoxy radicals used.And be somebody's turn to do
The selection of ratio can influence:(1) lifting of fire resistance, the lifting of (2) specific base material adherence (for example for composite,
Glass is tieed up or glass baseplate) appropriate crosslink density is provided and used with (3) improves the pliability after glue material film forming.
The fire-retardant polyester of present invention tool Formulas I structure, can be made by the following method：
(a) by least one dihydric alcohol, at least one saturation or unsaturated acid anhydride or acid andProgress polymerize instead
Should；
(b) further at least one saturation or unsaturated acid anhydride or acid and the product of step (a) are reacted；
(c) product of epoxy acrylate based compound or the siliceous compound of epoxy radicals and step (b) is modified instead
Should；And
(d) after step (c) reaction terminates, optionally, the siliceous compound of epoxy radicals is added, reaction is modified.
It is preferred that in above-mentioned (b) step being reacted using unsaturated acid anhydride or acid and the product of step (a).It is preferred that
It is to be modified reaction using epoxy acrylate based compound and the product of step (b) in above-mentioned (c) step.
Above-mentioned steps (a) products therefrom can be as shown in Formula Il：
Wherein residue A ' with residue B ', and polymerized unit number a, b are as previously described.
Above-mentioned steps (b) products therefrom can be as follows shown in formula III：
Wherein residue A ', residue B ' and residue B ", and polymerized unit number a, b, c are as previously described.
Above-mentioned steps (c) products therefrom can be as shown in following formula I：
Epoxy acrylate based compound in step (c) must can be included by taking GMA as an example
Product shown in following formula IV -1：
After step (c) terminates, optionally, the addition siliceous compound of epoxy radicals and the complete carboxyl reaction of unreacted, citing and
Say, above-mentioned epoxy acrylate based compound isAnd the siliceous compound of epoxy radicals isIt can must include product shown in following formula IV -2：
It is above-mentioned optionally the step of (d) terminate after, can still remain carboxyl, therefore, gained Formulas I product, wherein residue C'
It may be the same or different with residue C ", and it is siliceous each to stand alone as hydrogen, the residue of epoxy acrylate based compound or epoxy radicals
The residue of compound, and to ensure the progress of modified-reaction, C' and C " they can not be hydrogen simultaneously.
The preparation method of fire-retardant polyester of the present invention, with monomer (D) for reactant, compared to the system using DOPO as reactant
Journey, can obtain the fire-retardant polyester of higher phosphorus content, therefore flame resistance is preferable.
In the method for the present invention, the temperature range of polymerisation is visually selected to react raw material to determine；And determine to terminate
The time point of polymerisation, then judge according to the viscosity of products therefrom with whether acid value reaches be intended to scope.For viscosity, gained
Its range of viscosities of phosphorous unsaturated polyester (UP) is preferably G-Z (being tested with GARDNER viscosimeters), for example, can be G-H, I-J, K-L, M-
N, O-P, Q-R, R-S, T-U, V-W, W-X or X-Y；For acid value, the acid value scope of fire-retardant polyester of the invention is little
In 40, if lid acid value value is more than 40, gel (gelation) phenomenon easily occurs for obtained polyester.Therefore, it is good to obtain tool
The product of stability, stability in storage and painting work, the acid value scope for preferably controlling fire-retardant polyester is 20 to 40.This
Outside, the phosphorus content of fire-retardant polyester can be adjusted by one skilled in the art depending on anti-flammability demand, be had no specifically limited.
For example, it is however generally that if the flame resistance of suitable UL-94V0 grades need to be provided, phosphorus content is at least unsaturated polyester (UP) gross weight
More than 1.5%, preferably more than 2.0%, more preferably more than 2.5%.According to the present invention part preferred embodiment in, the resistance
The phosphorus content scope of combustion property polyester is 2.5% to 8%, such as, but not limited to 3.0%, 3.6%, 4% and 5%.
In the fire-retardant polyester of present invention tool Formulas I structure, each monomer consumption, which is preferably, meets following condition, to be produced obtained by profit
The stability and application of thing：The ratio between the molal quantity of monomer (A) and the total mole number of monomer (B1), (B2) and (C2) are 10：1 to
1：10, preferably 1：0.5 to 1：0.9, more preferably 1：0.6 to 1：0.8；The molal quantity and polymerized monomer (A) of monomer (C1),
(B1), (B2) and the ratio of the molal quantity of the polymer obtained by (C2) are 1：0.01 to 1：1.2, preferably 1：0.05 to 1：0.5, more
Good is 1：0.1 to 1：0.3；And monomer (B1) is 10 compared to the mole ratio of monomer (C2) with (B2)：1 to 1：10, preferably
For 5：1 to 1：5, more preferably 3：2 to 2：3.
Fire-retardant polyester of the present invention, with having good between radiation-hardenable and non-polar solven or monomer (such as styrene)
Good compatibility and base material have the advantages that good adherence, can be widely used for fire-retardant, coating, pigment (such as inorganic particle) point
The purposes such as scattered, adhesion promotion.
Therefore, the present invention also provides a kind of coating composition, and it is included：Fire-retardant polyester, the ethene system for having Formulas I structure are single
Body and polymerization initiator.Wherein, polymerization initiator (such as light initiator) is to be used to make vinyl monomer and composition
Contained unsaturated polyester (UP) produces cross-linked polymeric (such as UV photopolymerization) and forms solid product.With coating composition gross weight meter,
The consumption of vinyl monomer is 0% to 60%, preferable 0% to 55%, more preferably 10% to 40%, but is not limited；And polymerize
Reaction initiator consumption have no it is specifically limited, as long as being adequate to bring about polymerisation.With coating composition gross weight meter, resistance
The consumption of combustion property polyester is 40% to 100%, preferable 45% to 99.9%, more preferably 60% to 90%, but be not limited.
In the coating composition of the present invention, the species of vinyl monomer includes but is not limited to (methyl) acrylic compounds list
(methyl) acrylic ester monomer or its mixture of body, monofunctional or multiple functional radical, and preferably (methyl) acrylate
Class monomer.Monofunctional (methyl) acrylic ester monomer may be selected from such as, but not limited to, following group：Methyl methacrylate
Ester (methyl methacrylate, MMA), butyl methacrylate, 2- phenoxyethyl acrylates (2-phenoxy
Ethyl acrylate), ethoxyquin 2- phenoxyethyl acrylates (ethoxylated 2-phenoxy ethyl
Acrylate), 2- (2- ethoxy ethoxies) ethyl propylene acid esters (2- (2-ethoxyethoxy) ethyl acrylate), ring
Trimethylolpropane dimethoxym ethane acrylate (cyclic trimethylolpropane formal acrylate), carboxyethyl
Acrylate (carboxyethyl acrylate), 3,3,5- trimethylcyclohexyl acrylates (3,3,5-trimethyl
Cyclohexane acrylate), adjacent phenylphenoxy ethyl propylene acid esters (ortho-phenyl phenoxy ethyl
Acrylate), 2- (p- cumenyl-phenoxy group)-ethyl propylene acid esters (cumyl phenoxyl ethyl acrylate),
It is bay acid methacrylate (lauryl methacrylate), isooctyl acrylate (isooctyl acrylate), hard
Resin acid methacrylate (stearyl methacrylate), isodecyl acrylate (isodecyl acrylate), different ice
Piece methyl acrylate (isoborny methacrylate), Benzyl bases acrylate (benzyl acrylate), 2- hydroxyls
Ethylmethyl acrylate phosphate (2-hydroxyethyl metharcrylate phosphate), caprolactone base acrylic acid
Ester (caprolactone acrylate), hydroxy-ethyl acrylate (hydroxyethyl acrylate, HEA), methacrylic acid-
2- hydroxy methacrylates (2-hydroxyethyl methacrylate, HEMA) and its mixture.Its (methyl) propylene of multiple functional radical
Esters of gallic acid monomer may be selected from such as, but not limited to, following group：3- hydroxyl -2,2- dimethyl propyl -3- hydroxyl -2,2- dimethyl propylenes
Ester diacrylate (hydroxypivalyl hydroxypivalate diacrylate), 1,6 hexanediol diacrylate
(1,6-hexanediol diacrylate), ethoxyquin 1,6 hexanediol diacrylate (ethoxylated 1,6-
Hexanediol diacrylate), propylene glycol diacrylate (dipropylene glycol diacrylate), three rings
Decane Dimethanol Diacrylate (tricyclodecane dimethanol diacrylate), ethoxyquin DPG dipropyl
Olefin(e) acid ester (ethoxylated dipropylene glycol diacrylate), neopentylglycol diacrylate
(neopentyl glycol diacrylate), the third oxidation neopentylglycol diacrylate (propoxylated neopentyl
Glycol diacrylate), ethoxylated bisphenol A dimethylacrylates (ethoxylated bisphenol-A
Dimethacrylate), 2- methyl-1,3-propanediols diacrylate (2-methyl-1,3-propanediol
Diacrylate), ethoxyquin -2- methyl-1,3-propanediols diacrylate (ethoxylated 2-methyl-1,3-
Propanediol diacrylate), 2-butyl-2-ethyl-1,3-propanediol diacrylate (2-butyl-2-ethyl-1,
3-propanediol diacrylate), ethylene glycol dimethacrylate (ethylene glycol
dimethacrylate；EGDMA), dimethacrylate (diethylene glycol
Dimethacrylate), three (2- ethoxys) isocyanuric acid triacrylate (tris (2-hydroxy ethyl)
Isocyanurate triacrylate), pentaerythritol triacrylate (pentaerythritol triacrylate), second
Aoxidize trimethylolpropane trimethacrylate (ethoxylated trimethylolpropane triacrylate), the third oxidation
Trimethylolpropane trimethacrylate (propoxylated trimethylolpropane triacrylate), trihydroxy methyl
Propane trimethyl acrylic ester (trimethylolpropane trimethacrylate), tetramethylol methane tetraacrylate
(pentaerythritol tetraacrylate), ethoxyquin tetramethylol methane tetraacrylate (ethoxylated
Pentaerythritol tetraacrylate), two-trimethylolpropane tetra-acrylate (ditrimethylolpropane
Tetraacrylate), the third oxidation tetramethylol methane tetraacrylate (propoxylated pentaerythritol
Tetraacrylate), dipentaerythritol acrylate (dipentaerythritol hexaacrylate), tripropylene glycol
Dimethylacrylate (tripropylene glycol dimethacrylate), 1,4- butanediol dimethylacrylates
(1,4-butanediol dimethacrylate), 1,6-HD dimethylacrylate (1,6-hexanediol
Dimethacrylate), allylation cyclohexyldimethacrylate (allylated cyclohexyl
Dimethacrylate), dimethacrylate isocyanuric acid ester (isocyanurate dimethacrylate), ethoxylation
Trimethylol-propane trimethacrylate (ethoxylated trimethylolpropane trimethacrylate), third
Epoxide glycerol trimethacrylate (propoxylated glycerol trimethacrylate), three (propylene oxygen second
Base) isocyanuric acid ester (tris (acryloxyethyl) isocyanurate), trimethylolpropane trimethacrylate
(trimethylolpropane triacrylate) and its mixture.It is preferred that vinyl monomer is 2- Phenoxyethyls third
Olefin(e) acid ester (2-phenoxy ethyl acrylate), bay acid methacrylate (lauryl methacrylate), isodecyl
Base acrylate (isodecyl acrylate), isobornyl methacrylate (isoborny methacrylate), three
TRIM (trimethylolpropane trimethacrylate), pentaerythrite tetrapropylene acid
Ester (pentaerythritol tetraacrylate), ethoxylated trimethylolpropane trimethyl acrylic ester
(ethoxylated trimethylol propane trimeth acrylate), propoxylated glycerol trimethyl acrylic ester
(propoxylated glycerol trimethacrylate), trimethylolpropane trimethacrylate
(trimethylolpropane triacrylate) and its mixture.Commercially available vinyl monomer available for the present invention includes
The trade name EM223 that is produced by Eternal companies, EM328, EM2308, EM231, EM219, EM90, EM70, EM235,
EM2381、EM2382、EM2383、EM2384、EM2385、EM2386、EM2387、EM331、EM3380、EM241、EM2411、
EM242, EM2421 and EM265 person.
Optionally, other known paint ingredients or additive can be further included in the coating composition of the present invention, such as
It is silicon oxide compound, clay, defoamer, levelling agent, light stabilizer, antistatic additive, ultra-violet absorber, response type filler, non-
Response type filler, response type flexibility agent, elastomer or diluent etc..The usage and use of the known paint ingredient or additive
Amount is one skilled in the art see this specification disclosure after, can optionally be adjusted according to its usual knowledge
Person, has no specifically limited.
The present invention is further hereby illustrated with specific examples below.
Embodiment
Embodiment 1：Prepare the fire-retardant polyester (not siliceous) of tool formula IV -1
The diethylene glycol and 122 g of DPG of 627 g of addition first in 3 liters round bottom reaction bulbs,
Stirred 30 minutes at 70 DEG C.Afterwards, by several times addition 276 g maleic anhydride (i.e. monomer (B2)) and 1809 g 10- (2,
5- dicarboxypropyls) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is into reaction bulb, and the reaction at 200 DEG C
Until acid value is 65 to 75 and viscosity is 550 to 650 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Then,
0.165 g of Isosorbide-5-Nitrae-dihydroxy benzenes is added again into reaction bulb, and instills at 70 DEG C 323 g of Glycidyl methacrylate
Glyceride, is warming up to 95 DEG C and maintains constant temperature 3 hours afterwards, makes its reaction until acid value is that 25 to 30, viscosity is 750 to 850
(being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min) and the viscosity in 35% styrene (are glued for V-W with GARDNER
Degree measurement examination).Thus be made tool the structure of formula IV -1 through acrylate modified fire-retardant polyester.The flame retardance poly is obtained after measured
The phosphorus content of ester is 3.8%.
Embodiment 2：Have formula IV -1, the preparation of the flame-retardant polyester composition of IV-2 structures
The diethylene glycol and 122 g of propane diols of 627 g of addition first in 3 liters round bottom reaction bulbs, 70
Stirred 30 minutes at DEG C.Afterwards, 276 g of maleic anhydride (i.e. monomer (B2)) and 1809 g of 10- (2,5- are added by several times
Dicarboxypropyl) reaction is straight into reaction bulb, and at 200 DEG C for -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
To acid value be 65 to 75 and viscosity is 550 to 650 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Then, then
The Glycidyl methacrylate of 323 g of instillation is sweet into reaction bulb, and at 70 DEG C for Isosorbide-5-Nitrae-dihydroxy benzenes of 0.165 g of addition
Grease, is warming up to 95 DEG C and maintains constant temperature 3 hours afterwards, make its reaction until acid value be 25 to 30, viscosity be 750 to 850 (with
High-temperature viscosimeter is tested, #3,150 DEG C, 750 revs/min) and viscosity in 35% styrene is V-W (with GARDNER viscosity
Measurement examination).Afterwards, the temperature of reaction bulb is down to 45 DEG C, 60 g of γ-(methacryl is then instilled in reaction bulb
Oxygen) propyl trimethoxy silicane, and react 2 hours to acid value be 15 to 20 and the viscosity in 35% styrene be X-Y (with
GARDNER viscosimeters are tested).Thus the combination of the modified fire-retardant polyester comprising tool formula IV -1 and IV-2 structures is made
Thing.The phosphorus content for obtaining the fire-retardant polyester after measured is 3.73%.
Embodiment 3：Formula I fire-retardant polyester (not siliceous)
The diethylene glycol and 12.2 g of propane diols of 62.7 g of addition first in 3 liters round bottom reaction bulbs,
Stirred 30 minutes at 70 DEG C.Afterwards, 27.6 g of maleic anhydride (i.e. monomer (B2)) and 180.9 g of 10- are added by several times
(2,5- dicarboxypropyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is anti-into reaction bulb, and at 200 DEG C
Should be 65 to 75 until acid value and viscosity is 550 to 650 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Connect
, then add 0.165 g of Isosorbide-5-Nitrae-dihydroxy benzenes into reaction bulb, and instill at 70 DEG C 45.5 g of acrylic acid hydroxyl fourth
Base glycidol ether, is warming up to 95 DEG C and maintains constant temperature 3 hours afterwards, makes its reaction until acid value is that 25 to 30, viscosity is 750
Viscosity to 850 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min) and in 35% styrene for V-W (with
GARDNER viscosimeters are tested).Thus be made tool Formulas I structure through acrylate modified fire-retardant polyester.The resistance is obtained after measured
The phosphorus content of combustion property polyester is 3.65%.
Embodiment 4：Has the preparation of the flame-retardant polyester composition of Formulas I structure
The diethylene glycol and 12.2 g of propane diols of 62.7 g of addition first in 3 liters round bottom reaction bulbs,
Stirred 30 minutes at 70 DEG C.Afterwards, 27.6 g of maleic anhydride (i.e. monomer (B2)) and 180.9 g of 10- are added by several times
(2,5- dicarboxypropyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is anti-into reaction bulb, and at 200 DEG C
Should be 65 to 75 until acid value and viscosity is 550 to 650 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Connect
, then add 0.165 g of Isosorbide-5-Nitrae-dihydroxy benzenes into reaction bulb, and instill at 70 DEG C 45.5 g of acrylic acid hydroxyl fourth
Base glycidol ether, is warming up to 95 DEG C and maintains constant temperature 3 hours afterwards, makes its reaction until acid value is that 25 to 30, viscosity is 750
Viscosity to 850 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min) and in 35% styrene for V-W (with
GARDNER viscosimeters are tested).Afterwards, the temperature of reaction bulb is down to 45 DEG C, then in reaction bulb instill 6.0 g γ-
(methacryloxypropyl) propyl trimethoxy silicane, and react 2 hours be 15 to 20 and viscous in 35% styrene to acid value
Spend and (tested for X-Y with GARDNER viscosimeters).Thus the combination of the modified fire-retardant polyester comprising tool Formulas I structure is made
Thing.The phosphorus content for obtaining the fire-retardant polyester after measured is 3.58%.
Embodiment 5：Prepare the fire-retardant polyester (not siliceous) of tool formula IV -1
The diethylene glycol and 122 g of propane diols of 627 g of addition first in 3 liters round bottom reaction bulbs, 70
Stirred 30 minutes at DEG C.Afterwards, the phthalic anhydride of 148.1 g of gradation addition(i.e. monomer (B1)),
178 g of maleic anhydride (i.e. monomer (B2)) and 1809 g 10- (2,5- dicarboxypropyls) -9,10- dihydro-9-oxies
Miscellaneous -10- phospho hetero phenanthrenes -10- oxides into reaction bulb, and react at 200 DEG C until acid value is 65 to 75 and viscosity be 550 to
650 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Then, then 0.165 g of Isosorbide-5-Nitrae-dihydroxy benzenes is added
323 g of GMA is instilled into reaction bulb, and at 70 DEG C, 95 DEG C are warming up to afterwards and remains permanent
Temperature 3 hours, it is that 25 to 30, viscosity is 750 to 850 (to be tested with high-temperature viscosimeter, #3,150 DEG C, 750 until acid value to make its reaction
Rev/min) and viscosity in 35% styrene (tested for V-W with GARDNER viscosimeters).Thus the tool structure of formula IV -1 is made
Through acrylate modified fire-retardant polyester.The phosphorus content for obtaining the fire-retardant polyester after measured is 3.7%.
Embodiment 6：Have formula IV -1, the preparation of the flame-retardant polyester composition of IV-2 structures
The diethylene glycol and 122 g of propane diols of 627 g of addition first in 3 liters round bottom reaction bulbs, 70
Stirred 30 minutes at DEG C.Afterwards, the phthalic anhydride (i.e. monomer (B1)) of 148.1 g of gradation addition, 178 g of Malaysia
Acid anhydrides (i.e. monomer (B2)) and 1809 g of miscellaneous -10- phospho hetero phenanthrenes of 10- (2,5- dicarboxypropyls) -9,10- dihydro-9-oxies -
10- oxides are reacted until acid value is 65 to 75 and viscosity is 550 to 650 (viscous with high temperature into reaction bulb, and at 200 DEG C
Degree measurement examination, #3,150 DEG C, 750 revs/min).Then, then 0.165 g of Isosorbide-5-Nitrae-dihydroxy benzenes is added into reaction bulb, and
The GMA of 323 g of instillation, is warming up to 95 DEG C and maintains constant temperature 3 hours, make it afterwards at 70 DEG C
Reaction until acid value be 25 to 30, viscosity be 750 to 850 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min) and
Viscosity in 35% styrene (is tested) for V-W with GARDNER viscosimeters.Afterwards, the temperature of reaction bulb is down to 45 DEG C, then
Instill 60 g γ-(methacryloxypropyl) propyl trimethoxy silicane in reaction bulb, and react 2 hours to acid value be 15
Viscosity to 20 and in 35% styrene (is tested) for X-Y with GARDNER viscosimeters.Thus be made comprising tool formula IV -1 and
The composition of the modified fire-retardant polyester of IV-2 structures.The phosphorus content for obtaining the fire-retardant polyester after measured is 3.7%.
Embodiment 7：Prepare the fire-retardant polyester (not siliceous) of tool formula IV -1
The diethylene glycol and 48.6 g of DPG of 169.5 g of addition in 3 liters round bottom reaction bulbs, 70
Stirred 30 minutes at DEG C.Afterwards, 101.4 g of phthalic anhydride (i.e. monomer (B1)) and 1000.1 g of 10- are added
(2,5- dicarboxypropyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is anti-into reaction bulb, and at 200 DEG C
Should be 65 to 75 until acid value and viscosity is 550 to 650 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Connect
, then add 0.165 g of Isosorbide-5-Nitrae-dihydroxy benzenes into reaction bulb, and titrate at 70 DEG C 680.4 g of metering system
Acid glycidyl ester, is warming up to 95 DEG C and maintains constant temperature 3 hours afterwards, makes its reaction until acid value is that 25 to 30, viscosity is 750
Viscosity to 850 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min) and in 35% styrene for V-W (with
GARDNER viscosimeters are tested).Thus gathering through acrylate modified phosphorous unsaturation for the not siliceous structure of tool formula IV -1 is made
Ester.It is 4.1% to obtain the phosphorous unsaturated polyester (UP) phosphorus content after measured.
Embodiment 8：Have formula IV -1, the preparation of the flame-retardant polyester composition of IV-2 structures
The diethylene glycol and 48.6 g of DPG of 169.5 g of addition in 3 liters round bottom reaction bulbs, 70
Stirred 30 minutes at DEG C.Afterwards, 101.4 g of phthalic anhydride (i.e. monomer (B1)) and 1000.1 g of 10- are added
(2,5- dicarboxypropyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is anti-into reaction bulb, and at 200 DEG C
Should be 65 to 75 until acid value and viscosity is 550 to 650 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Connect
, then add 0.165 g of Isosorbide-5-Nitrae-dihydroxy benzenes into reaction bulb, and titrate at 70 DEG C 680.4 g of metering system
Acid glycidyl ester, is warming up to 95 DEG C and maintains constant temperature 3 hours afterwards, makes its reaction until acid value is that 25 to 30, viscosity is 750
Viscosity to 850 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min) and in 35% styrene for V-W (with
GARDNER viscosimeters are tested).Thus be made not siliceous tool Formulas I structure through acrylate modified phosphorous unsaturated polyester (UP).
Afterwards, the temperature of reaction bulb is down to 45 DEG C, 60 g γ-(methacryloxypropyl) propyl group three is then instilled in reaction bulb
Methoxy silane, and react 2 hours to acid value be 15 to 20 and the viscosity in 35% styrene is X-Y (with GARDNER viscosity
Measurement examination).Thus be made siliceous tool formula IV -1, IV-2 structures through acrylate modified phosphorous unsaturated polyester (UP).Through surveying
Surely it is 4.0% to obtain the phosphorous unsaturated polyester (UP) phosphorus content.
Embodiment 9：Prepare the fire-retardant polyester (not siliceous) of tool formula IV -1
The diethylene glycol and 63.1 g of DPG of 220.0 g of addition in 3 liters round bottom reaction bulbs, 70
Stirred 30 minutes at DEG C.Afterwards, the phthalic anhydride and 256.2 g of 10- (2,5- dicarboxyls third of 577.6 g of addition
Base) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide reacted until acid value is into reaction bulb, and at 200 DEG C
65 to 75 and viscosity be 450 to 550 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Then, then 0.165 is added
G Isosorbide-5-Nitrae-dihydroxy benzenes titrate 883.2 g of GMA into reaction bulb, and at 70 DEG C, it
After be warming up to 95 DEG C and maintain constant temperature 3 hours, it is that 25 to 30, viscosity is 550 to 650 (viscous with high temperature until acid value to make its reaction
Degree measurement examination, #3,150 DEG C, 750 revs/min) and viscosity in 35% styrene (measured for S-T with GARDNER viscosity
Examination).Thus be made the not siliceous structure of tool formula IV -1 through acrylate modified phosphorous unsaturated polyester (UP).After measured must this contain
Phosphorus unsaturated polyester (UP) phosphorus content is 1.09%.
Embodiment 10：Has the preparation of the flame-retardant polyester composition of Formulas I structure
The diethylene glycol and 48.6 g of DPG of 169.5 g of addition in 3 liters round bottom reaction bulbs, 70
Stirred 30 minutes at DEG C.Afterwards, 101.4 g of phthalic anhydride (i.e. monomer (B1)) and 1000.1 g of 10- are added
(2,5- dicarboxypropyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is anti-into reaction bulb, and at 200 DEG C
Should be 65 to 75 until acid value and viscosity is 550 to 650 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min).Connect
, then add 0.165 g of Isosorbide-5-Nitrae-dihydroxy benzenes into reaction bulb, and titrate at 70 DEG C 680.4 g of metering system
Acid glycidyl ester, is warming up to 95 DEG C and maintains constant temperature 3 hours afterwards, makes its reaction until acid value is that 25 to 30, viscosity is 750
Viscosity to 850 (being tested with high-temperature viscosimeter, #3,150 DEG C, 750 revs/min) and in 35% styrene for V-W (with
GARDNER viscosimeters are tested).Thus be made not siliceous tool Formulas I structure through acrylate modified phosphorous unsaturated polyester (UP).
Afterwards, the temperature of reaction bulb is down to 45 DEG C, 73.2 g of 2- (3,4- 7-oxa-bicyclo[4.1.0 base) is then instilled in reaction bulb
Ethyl triethoxysilaneAnd react 2 hours to acid value be 15 to 20 and in 35% benzene
Viscosity in ethene (is tested) for X-Y with GARDNER viscosimeters.Thus changing through acrylate for siliceous tool Formulas I structure is made
The phosphorous unsaturated polyester (UP) of property.It is 3.7% to obtain the phosphorous unsaturated polyester (UP) phosphorus content after measured.
Anti-flammability, film forming test, adherence test are tested with film hardness
Fire-retardant polyester made from embodiment 1 to embodiment 10 is subjected to flame retardant test, film forming test, adherence test
Tested with film hardness.Wherein, flame retardant test is that resin is tested according to UL94 standard pins；Film forming test is with such as lower section
Formula is carried out：Mix the modified fire-retardant polyester, the styrene of 35 parts by weight, the cobalt iso-octoate of 6 parts by weight and 1 of 65 parts by weight
The methylethyl ketone peroxide (Methyl Ethyl Ketone Peroxide, MEKPO) of parts by weight, PET is coated on by gained mixture
On base material and to solidify to form thickness be 500 microns of film, its film forming smooth degree is observed, outward appearance is preferred without warpage person；Adherence
Property test be to carry out as follows：Mix modified fire-retardant polyester, the cobalt iso-octoate of 6 parts by weight and 1 of 100 parts by weight
The methylethyl ketone peroxide (Methyl Ethyl Ketone Peroxide, MEKPO) of parts by weight, two panels is coated on by gained mixture
The scope face that same compound material (a height of 25cm*25cm*3mm of the long wide * of *) is formed in the wide 20cm of long 25cm of a coincidence end points
A temporary material (PET film) is inserted to patch, and in veneer other parts, is made after its hardening, temporary material formation drawing area is removed, to draw
Excellent the lacking of the method test density pulled out, excellent scarce degree one is divided into three-level:Excellent (do not have, almost do not have or slightly tear glue surface),
Good (certain limit tear glue surface), poor (largely tear or glue surface and composite are kept completely separate glue surface)；And film hardness is real
Test is to utilize JIS K5400 standard methods test pencil hardness (base material is polyethylene terephthalate (PET)/plank), institute
Obtain result as shown in table 1：
Table 1
As shown in table 1, no matter whether siliceous fire-retardant polyester and flame-retardant polyester composition of the present invention be, is more than in phosphorus content
Under conditions of 1.5%, it can all be tested by the resistance to combustion of UL-94V0 grades, possess excellent fire-retardancy, and film forming during for coating
Property good and made film hardness be not less than 4H.And siliceous flame-retardant polyester composition is in adherence test result
It is excellent.
Above-described embodiment be only illustrative the present invention principle and its effect, and illustrate the present invention technical characteristic,
Not for the protection category of the limitation present invention.It is any to be familiar with this technology person in the know-why and spirit without prejudice to the present invention
Under, can unlabored change or arrangement, the scope that the category present invention is advocated.Therefore, the scope of the present invention is
As listed by claims institute claim.
Claims (9)
1. a kind of fire-retardant polyester, it has Formulas I structure：
Wherein each A' stands alone as residue of dihydric alcohol, and each B' and each B " may be the same or different and each stand alone as saturation or not
The residue of saturation acid anhydrides or acid, C' and C " may be the same or different and each stand alone as hydrogen, epoxy acrylate based compound
Residue, restrictive condition is that C' and C " non-concurrent is hydrogen, and wherein a is 1 to 30 integer, and b is 1 to 30 integer, and c is 1 to 15
Integer, and wherein the fire-retardant polyester has 20 to 40 acid value.
2. fire-retardant polyester as claimed in claim 1, the wherein dihydric alcohol be selected from by ethylene glycol, diethylene glycol, propane diols,
DPG, neopentyl glycol, polyethylene glycol, styrene glycol, hexylene glycol, butanediol, 1- phenyl -1,2- ethylene glycol, 2-
Bromo- 2- nitros -1,3- propane diols, 2- methyl -2- nitro -1,3- propane diols, double methylol diethyl malonates,
The group that hydroquinones and 3,6- dithia -1,8- ethohexadiols and combinations thereof are constituted.
3. fire-retardant polyester as claimed in claim 1, wherein the saturation acid anhydrides or acid be selected from by phenylsuccinic acid, benzyl malonic acid,
3- phenyl glutaric acid, 1,4- diethylamino phenyls acid, 1,2- diethylamino phenyls acid, oxalic acid, malonic acid, succinic acid, equal benzene tertacarbonic acid's dianhydride,
3,3', 4,4'- benzophenone-tetracarboxylic dianhydride, naphthalene dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid acid anhydride, cyclobutanetetracarboxylic dianhydride, 2,3- anthracenes
Dicarboxylic anhydride, 3,4,9,10- tetracarboxylic anhydrides, 1,2,3,4- butane tetracarboxylics acid dianhydride, the tetracarboxylic dianhydride of 1,2,3,4- rings penta, phenyl penta 2
Acid anhydrides, adipic anhydride, 3,3- dimethylated pentanedioic acids acid anhydride, phenylsuccinic acid acid anhydride, hexahydrophthalic anhydride and selected from tool formula: And combinations thereof the group that is constituted, wherein R1And R2Each stand alone as H or be substituted or be unsubstituted
C1 to C15 alkyl.
4. fire-retardant polyester as claimed in claim 1, the wherein unsaturated acid anhydride or acid be selected from by And combinations thereof the group that is constituted, wherein R1And R2Each stand alone as H or the C1 that is substituted or is unsubstituted is to C15 hydrocarbon
Base.
5. fire-retardant polyester as claimed in claim 1, wherein the epoxy acrylate based compound are (methyl) acrylic acid
Ethylene oxidic ester, 3,4- epoxycyclohexyl-methyls (methyl) acrylate orOr its group
Close, wherein R3For H or methyl, R4Straight or branched alkylidene for C1 to C15 or the group selected from following group：
Wherein n is 1 to 15 integer, and m is 1 to 10 integer, and R is H or methyl, and T is
6. a kind of coating composition, comprising the fire-retardant polyester as any one of claim 1 to 5, vinyl monomer and
Polymerization initiator.
7. a kind of method for preparing the fire-retardant polyester as described in any in claim 1 to 5, it comprises the following steps：
(a) by least one dihydric alcohol, at least one saturation or unsaturated acid anhydride or acid andCarry out polymerisation；
(b) further at least one saturation or unsaturated acid anhydride or acid and the product of step (a) are reacted；
(c) product of epoxy acrylate based compound or the siliceous compound of epoxy radicals and step (b) is modified reaction；And
(d) after step (c) reaction terminates, optionally the siliceous compound of epoxy radicals is added, reaction is modified.
8. method as claimed in claim 7, wherein step (b) are by least one unsaturated acid anhydride or acid and step (a)
Product reacts.
9. such as the method for claim 7 or 8, wherein step (c) is the production by epoxy acrylate based compound and step (b)
Thing is modified reaction.
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| CN201710041782.7A CN106947070A (en) | 2017-01-20 | 2017-01-20 | Fire-retardant polyester |
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| CN107353371A (en) * | 2017-07-15 | 2017-11-17 | 北京恒安外加剂有限责任公司 | high-performance water reducing agent and preparation method thereof |
| CN109337057A (en) * | 2018-09-28 | 2019-02-15 | 韶关市合众化工有限公司 | A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force |
| CN110183617A (en) * | 2019-07-01 | 2019-08-30 | 黄山正杰新材料有限公司 | A kind of transparent powder that wearability is excellent 50:50 polyester resin and the preparation method and application thereof |
| CN110305569A (en) * | 2019-07-17 | 2019-10-08 | 浙江光华科技股份有限公司 | A kind of polyester resin and preparation method thereof based on phenylsuccinic acid acid anhydride |
| CN110724250A (en) * | 2019-09-30 | 2020-01-24 | 浙江恒澜科技有限公司 | Preparation method and application of aromatic alcohol modified polyester chip |
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| CN107353371A (en) * | 2017-07-15 | 2017-11-17 | 北京恒安外加剂有限责任公司 | high-performance water reducing agent and preparation method thereof |
| CN109337057A (en) * | 2018-09-28 | 2019-02-15 | 韶关市合众化工有限公司 | A kind of Organic fluoride boron and the hydrophobic flame-retarded unsaturated polyester resin of epoxy-modified high adhesion force |
| CN110183617A (en) * | 2019-07-01 | 2019-08-30 | 黄山正杰新材料有限公司 | A kind of transparent powder that wearability is excellent 50:50 polyester resin and the preparation method and application thereof |
| CN110183617B (en) * | 2019-07-01 | 2021-09-07 | 黄山正杰新材料有限公司 | A transparent powder with excellent wear resistance is prepared from (A) 50: 50 polyester resin and preparation method and application thereof |
| CN110305569A (en) * | 2019-07-17 | 2019-10-08 | 浙江光华科技股份有限公司 | A kind of polyester resin and preparation method thereof based on phenylsuccinic acid acid anhydride |
| CN110724250A (en) * | 2019-09-30 | 2020-01-24 | 浙江恒澜科技有限公司 | Preparation method and application of aromatic alcohol modified polyester chip |
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