CN107739433A - A kind of terminal hydroxy group phosphorous-containing polyester, preparation method and application and a kind of halogen-free flameproof activeness and quietness epoxy composite material - Google Patents
A kind of terminal hydroxy group phosphorous-containing polyester, preparation method and application and a kind of halogen-free flameproof activeness and quietness epoxy composite material Download PDFInfo
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- CN107739433A CN107739433A CN201710858351.XA CN201710858351A CN107739433A CN 107739433 A CN107739433 A CN 107739433A CN 201710858351 A CN201710858351 A CN 201710858351A CN 107739433 A CN107739433 A CN 107739433A
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Polyesters Or Polycarbonates (AREA)
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Abstract
The invention provides a kind of terminal hydroxy group phosphorous-containing polyester and preparation method thereof, the polyester is after being esterified by dihydric alcohol and binary acid or its carboxylate that methylene number is 28, to be obtained through polycondensation reaction, number-average molecular weight Mn is 1.8 × 10 3‑5.0×104g·mol‑1.Present invention also offers the method that halogen-free flame-proof toughening epoxy composite material is prepared using the polyester, by by 1 30 parts of weight of polyester, 60 90 parts of parts by weight epoxy resin and 10 40 parts of parts by weight curing agent are mixed to prepare, obtained composite both preferably maintains epoxy matrix glass transition temperature, the transparency and heat resistance, also assign epoxy resin excellent fire resistance and mechanical property, and material impact intensity, tensile strength and bending strength are increased dramatically simultaneously, method technique is simple, cost is low, realize that epoxy composite material is fire-retardant simultaneously under few additive, enhancing and toughness reinforcing, epoxy resin application is widened significantly.
Description
Technical field
The invention belongs to phosphorous-containing polyester and its preparation and application field.More particularly to a kind of terminal hydroxy group phosphorous-containing polyester, its system
Preparation Method, the method that halogen-free flameproof activeness and quietness epoxy composite material is prepared using the polyester, and a kind of enhancing of halogen-free flameproof
Flexibilizing epoxy composite.
Background technology
Epoxy resin (EP) is a kind of important thermosetting resin, has excellent adhesive property, anti-wear performance, mechanical property
Energy, electrical insulation capability, chemical stability, high and low temperature resistance, and it has that cure shrinkage is low, easy processing shaping and into
The advantages that this is cheap, it is widely used in Aero-Space, engineering construction, automobile ship and the field such as electric, especially in structure
The fields such as composite, electric, coating and binder, EP turn into indispensable important materials.However, due to epoxy
It is in tridimensional network after solidification, crosslink density is high, and molecule interchain lacks slip, and internal stress is big, causes epoxy curing compound fragility
It is larger, and the oxygen index (OI) (LOI) of epoxy resin only has 20% or so, belongs to combustible material.The shortcomings that epoxy resin is inflammable causes
It is dfficult to apply to some fields for requiring high fire-retardance and high tenacity, such as automobile, Aero-Space and electronic apparatus field, and is
The fire retardant for improving epoxy anti-flammability and adding, because it is poor with epoxy matrix phase tolerance, dispersed bad and interface interaction power
The problems such as, inevitably lead to material mechanical performance and further deteriorate.
Therefore there is an urgent need to find new high-efficiency multi-function epoxy modifying agent, the same of the excellent anti-flammability of material is being assigned
When can keep or even be lifted the mechanical property of material, widen the use range of epoxy resin.
In terms of epoxy resin roughening, prior art and document disclose and report a variety of epoxy resin toughened, to be related to increasing
Tough dose comprising thermoplastic resin, block copolymer, core-shell particles, dissaving polymer, rubber elastomer, Nano filling particle,
Carbon material or its modifier etc..Chinese patent such as Application No. 201110211075.0 discloses a kind of block copolymer-modified
Epoxy resin；The Chinese patent of Application No. 201380052928.8 discloses the solid ring oxygen tree that a kind of core shell rubbers are modified
Fat；The Chinese patent of Application No. 201310415460.6 discloses a kind of the epoxy resin toughened of asphalt modification；Application No.
201610202906.0 Chinese patent disclose it is a kind of selected from polyether sulfone and its derivative, PPG and its derivative and
It is one or more of epoxy resin toughened in polyether-ketone and its derivative.Although prior art provides a variety of toughening modifyings
Epoxy resin, but while epoxy resin toughened toughness improves, it is fixing that the tensile strength of material, modulus etc. but receive one
Ring.
In terms of ethoxyline resin antiflaming, add fire retardant be a kind of cost it is cheap, it is simple to operate imparting epoxy material high resistant
The method of combustion property.Phosphorus flame retardant is the ignition-proof element being most widely used after the halogenated flame retardant, phosphorous structure of functional groups
It is various, easy prepare, toxicity is low and secondary pollution is small, be introduced into epoxy resin structural that fire resistance, electrical property can be prepared is excellent
Good and environment-friendly product.Has the application of phosphonium flame retardant in the epoxy of more patent and document report.
The Introduction To Cn Patent of Application No. 200710164764.4 is a kind of phosphorous and nitrogen macromolecule expansion type flame retardant and its preparation
Method, dosage must can be only achieved more excellent anti-flammability to phosphonium flame retardant prepared by this method up to 30wt% in the epoxy
Can, flame retarding efficiency is low；The Chinese patent of Application No. 200910189733.3 report several small molecule phosphonium flame retardants and its
The problems such as leaching and mechanical property deterioration be present in preparation method, these small molecule phosphonium flame retardants.
In order that material obtains certain anti-flammability and excellent mechanical performance, generally require to add fire retardant and increasing simultaneously
Tough dose, but the addition of a variety of modifying agent can cause epoxy resin viscosity to become big, processability is deteriorated.In addition, these modifying agent can
There can be the phenomenon that effect cancels each other, it is final to cause epoxy product to be difficult to the requirement for meeting relevant art field.At present
Few work report researchs solve the problems, such as the inflammable and poor toughness of epoxy resin simultaneously by one-component, efficient more work(
The design synthesis of energy epoxy modifying agent is a big science difficult point of the fire-retardant toughened modification of epoxy.
The content of the invention
The invention provides a kind of terminal hydroxy group phosphorous-containing polyester and preparation method thereof, also directed to the fire-retardant toughened technology of existing epoxy
The defects of existing, there is provided be added to by the use of the terminal hydroxy group phosphorous-containing polyester as modifying agent in epoxy, while realize the resistance of material
Combustion and toughness reinforcing, obtain the method for the epoxy composite material that comprehensive mechanical property is excellent, fire resistance is good, overcome existing realization
The defects of lifting of epoxy anti-flammability, toughness enhancing need to add a variety of modifying agent, solves existing for existing epoxide resin material
The problem of fire-retardant toughened efficiency is low, matrix and modifying agent poor compatibility cause material mechanical performance and hot property declines.
The present invention realizes particular by following technical scheme：
Terminal hydroxy group phosphorous-containing polyester provided by the invention, the copolyesters are by following I, II or I, the III construction unit group represented
Into：
In formula, R1RepresentIn
It is any；N is 2-8 integer；
In formula, R2For any of H atom, methyl, methylene, phenyl, benzyl and phenylacetylene base；It is preferred that R2It is former for H
Son, phenyl, phenylacetylene base, more preferably R2For H atom, phenylacetylene base.
Further, when I construction unit monomer is entered with II construction unit monomer by a mole equivalent proportion 1.005-1.05
Row feeds intake, and obtained phosphorous-containing polyester intrinsic viscosity [η] is 0.46-0.98dL/g, and number-average molecular weight [Mn] is 5000g/mol-
50000g/mol；I construction unit monomer feeds intake with III construction unit monomer by a mole equivalent proportion 1.005-1.05, obtains
Phosphorous-containing polyester intrinsic viscosity [η] is 0.25-0.48dL/g, and number-average molecular weight [Mn] is 1800g/mol-8000g/mol.
Prepare above-mentioned terminal hydroxy group phosphorous-containing polyester, its method be by dihydric alcohol and binary acid that methylene number is 2-8 or
Its carboxylate, after being esterified using the direct esterification or ester-interchange method of routine, catalyst is added according to conventional proportions, is passed through
Polycondensation reaction can obtain hydroxy-end capped phosphor-containing flame-proof polyester.
The alkoxide component added in reaction system is any of following structure, preferably a, b, f, h structures alones, more preferably
N is 5,6,7,8 monomer.
Acid constituents is any of following structure, preferably a, c, e, k.
Polyester polycondensation catalyst used is zinc acetate, manganese acetate, acetic acid in above-mentioned terminal hydroxy group phosphorous-containing polyester preparation method
At least one of cobalt, antimony oxide, antimony glycol or titanate esters, preferably zinc acetate, antimony oxide, antimony glycol, titanium
Sour four butyl esters.
Further, wherein as alkoxide component dihydric alcohol and as the binary acid of acid constituents or its carboxylate according to mole
Equivalents ratio is 1.005：1-1.05:1 feeds intake, and preferably alkoxide component and acid constituents molar equivalent ratio are 1.005：1-1.02:1 throws
Material.According to preferred alkoxide component, acid constituents structure and preferred molar equivalent in the above method than feed intake be prepared it is phosphorous poly-
The intrinsic viscosity of ester is 0.30-0.70dL/g, number-average molecular weight 3000g/mol-40000g/mol.
The method that halogen-free flameproof activeness and quietness epoxy resin is prepared by above-mentioned terminal hydroxy group phosphorous-containing polyester, it is by described end
Hydroxyl phosphorous-containing polyester is mixed with epoxy resin, and mixture is well mixed, very by heating stirring with curing agent afterwards to being completely dissolved
Poured into after empty de-bubble in mould and solidify and obtain.
Further, it is that the terminal hydroxy group phosphorous-containing polyester of 1-30 parts by weight is first added to the epoxy resin of 60-90 parts by weight
In, mixture is well mixed by heating stirring with the curing agent of 10-40 parts by weight afterwards to being completely dissolved, and is fallen after froth in vacuum
Enter in mould and solidify and be made.
Epoxy resin used is bisphenol A type epoxy resin, bisphenol f type epoxy resin, the shrink of more phenolic in the above method
Glycerin ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine epoxy
Any of resin, epoxidation of olefins compound, heterocyclic-type epoxy resin and mixed type epoxy resin are several；It is preferred that bis-phenol
Any of A types epoxy resin, bisphenol f type epoxy resin and more phenolic tetraglycidel ether epoxy resins are several, more excellent
Select bisphenol A type epoxy resin, more phenolic tetraglycidel ether epoxy resins.
Curing agent used is aliphatic polyol amine type curing agent, cycloaliphatic polyols amine type curing agent, aromatic amine in the above method
Type curing agent, acid anhydride type curing agent, polyamide-type hardener, cyanogen amine curing agent, imidazole curing agent and modified amine are consolidated
Any of agent is several；The polynary amine type curing agent of preferred fat, cycloaliphatic polyols amine type curing agent, the solidification of fragrant amine type
Any of agent, acid anhydride type curing agent, imidazole curing agent and modified amine curing agent, more preferably fragrant amine type solidification
Agent, acid anhydride type curing agent, imidazole curing agent.
Present invention also offers a kind of halogen-free flameproof activeness and quietness epoxy composite material, is by above-mentioned 1- by weight
30 parts of hydroxy-end capped phosphorous-containing polyesters, 60-90 parts epoxy resin, 10-40 parts curing agent composition, the tensile strength of the compound are
45-95MPa, unnotched impact strength 10-45KJ/m2, bending strength 80-168MPa, limited oxygen index 22.0-
43.5%, vertical combustion grade is V1-V-0 levels.
Further, when the parts by weight of the terminal hydroxy group phosphorous-containing polyester of addition are preferably 2-15 parts, described nothing
The fire-retardant activeness and quietness epoxy composite material of halogen by the parts by weight hydroxy-end capped phosphorous-containing polyester of meter 2-15 parts and 60-90 parts epoxy resin and
10-40 parts curing agent forms, and the tensile strength of the compound is 55-90MPa, unnotched impact strength 12-40KJ/m2, it is curved
Qu Qiangdu is 100-160MPa, limited oxygen index 24.0-36.0%；Vertical combustion grade is V-1-V-0 levels.
Direct esterification or ester-interchange method of the present invention are conventional method, and catalyst proportion is conventional proportions, example
Such as, its processing step and condition can specifically use following methods：
Direct esterification：Polyester monocase and catalyst are added by proportioning in reaction vessel, pressurization is warming up to 180-200 DEG C
Carry out esterification 3-5h；After esterification terminates, in 200-230 DEG C of polycondensation reaction 0.5-2h under low vacuum, then under a high vacuum
In 210-240 DEG C of polycondensation 3-6h, target polyesters are obtained.
Ester-interchange method：Polyester monocase and catalyst are added by proportioning in reaction vessel, normal pressure carries out ester in 160-180 DEG C
Exchange reaction 3-5h；After ester exchange terminates, in 190-230 DEG C of polycondensation 0.5-2h under low vacuum, then under a high vacuum in 200-
240 DEG C of polycondensation 3-6h, obtain target polyesters.
The present invention compared with prior art, has advantages below：
(1) terminal hydroxy group phosphorous-containing polyester provided by the invention, the preferable heat endurance and molecular structure itself having
The rigidity that phenyl ring is brought, and can be by adjusting methylene number come regulatory molecule chain flexibility so that it has extensive
Purposes, during especially as composite modification agent, enable to the heat endurance of composite and thermomechanical property obtain compared with
Good holding.
(2) terminal hydroxy group phosphorous-containing polyester preparation method provided by the invention, controllability is high, and simple to operate, cost is cheap, and two
Acid constituents can be prepared by bio-based source raw material, thus can reduce the dependence to petroleum resources to a certain extent,
And then reduce production cost.
(3) hydroxyl telechelic polyester prepared by the present invention is added in epoxy as multi-functional epoxy modifying agent, can obtain
Toughness, intensity improve simultaneously and the epoxy composite material of high flame retardant, realizes and is assigning the same of epoxy material high flame retardant
When mechanical property not only without decline do not increase on the contrary, also, only by add one-component realize epoxy resin it is fire-retardant,
Enhancing and toughness reinforcing, reduce the addition species and dosage of modifying agent, have good economic benefit.
(4) phosphorous-containing polyester prepared by the present invention has good compatibility with epoxy matrix, it is not necessary to additionally adds solvent, directly
Connecting heating stirring can just make it be uniformly dispersed in epoxy matrix, and it can produce solidification by terminal hydroxy group and epoxide group
Cross-linking reaction is embedded into epoxy network.Flexible polyester molecule segment is uniformly embedded into cross-linked network by reaction so that is handed over
Molecular chain length increase between the overall crosslinking points of networking network, suitably increases while the homogeneity of cross-linked network is destroyed
The compliance of cross-linked network and the locomitivity of cross-linked network, and be closely wound between strand and cross-linked network, formed similar
The structure of semi-intercrossing network, both obtain tensile strength, elongation at break, shock resistance and the bending property of gained compound
Obvious raising was obtained, makes its glass transition temperature and Modulus Strength decline very small again.
For example, the biphenyl dioxy using method provided by the present invention, only 2.5 parts or so of addition weight epoxy number
Hexanol monomer polymerize obtained terminal hydroxy group phosphorous-containing polyester, the tensile strength of sample, elongation at break, tension failure with DDP monomers
Toughness, impact strength and bending strength are just substantially improved compared to pure sample, have been respectively increased 20.3%, 30.8%,
71.1%, 158% and 40.7%, limited oxygen index (LOI) is promoted to 29.5% from 26.5%, passes through vertical combustion (UL-94)
V-1 levels.
(5) hydroxyl telechelic polyester and the compatibility of epoxy matrix that prepared by the present invention are good, and the shape of subparticipation curing network
Into, it is not easy to migrate, can guarantee that Flame Retardancy can durability, overcome small molecule phosphonium flame retardant heat decomposition temperature it is low, with
Polymeric matrix poor compatibility and it is easy to migrate the shortcomings that.Compared with existing organic phosphorus flame retardant, its flame retarding efficiency is high, is not required to
Largely to add, during for epoxy resin, when the phosphorus content of modifying agent is only 0.5 parts by weight or so, epoxy resin is solid
The limited oxygen index of compound has brought up to 34.5% or so by 26.5%, and vertical combustion grade has reached UL-94V-0 levels.Now,
Epoxy curing compound still has mechanical property more more preferable than pure epoxy.
(6) epoxy composite material preparation method provided by the invention can by adjusting the ratio of modifying agent and epoxy resin,
To obtain the epoxy resin cured product for meeting different anti-flammabilitys and mechanical property requirements.
Brief description of the drawings
Fig. 1 is the proton nmr spectra of the synthetically prepared monomer biphenyl dioxy hexanol of the embodiment of the present invention 1.At each chemical shift
Go out peak position and can find corresponding ownership, and integral area is consistent from theoretical different chemical environment numbers of hydrogen atoms, says
Bright successfully prepare has synthesized biphenyl dioxy hexanol.
Fig. 2 is the proton nmr spectra of the synthetically prepared monomer phenylacetylene base diethyl phosphite of the embodiment of the present invention 11.Respectively
Going out peak position and can find corresponding ownership at chemical shift, and integral area and theoretical different chemical environment numbers of hydrogen atoms
It is consistent, illustrates successfully to prepare and synthesized phenylacetylene base diethyl phosphite.
Fig. 3 is that the nuclear-magnetism of the synthetically prepared monomer 4,4 ' of the embodiment of the present invention 12-bis- (6- hydroxyls hexyloxies) tolans is total to
The hydrogen that shakes is composed.Going out peak position and can find corresponding ownership at each chemical shift, and integral area and theoretical different chemical environments
Numbers of hydrogen atoms is consistent, and illustrates successfully to prepare and has synthesized 4,4 '-bis- (6- hydroxyls hexyloxy) tolans.
Fig. 4 is the nuclear magnetic resonance of the synthetically prepared monomer 4,4 ' of the embodiment of the present invention 14-bis- (6- hydroxyls hexyloxies) diphenyl ether
Hydrogen is composed.Going out peak position and can find corresponding ownership at each chemical shift, and integral area and theoretical different chemical environment hydrogen
Atom number is consistent, and illustrates successfully to prepare and has synthesized 4,4 '-bis- (6- hydroxyls hexyloxy) diphenyl ether.
Fig. 5 is the proton nmr spectra of terminal hydroxy group phosphorous-containing polyester prepared by the embodiment of the present invention 1.3.65ppm is hydroxyl in figure
The chemical shift of hydrogen on base, going out peak position and can find corresponding ownership at other each chemical shifts, and integral area with
Theoretical different chemical environment numbers of hydrogen atoms are consistent, and illustrate successfully to prepare and have synthesized terminal hydroxy group phosphorous-containing polyester.
Fig. 6 is that halogen-free flameproof activeness and quietness epoxy composite material prepared by the embodiment of the present invention 30 is quenched the SEM-EDX of section
P elements Surface scan figure.From the figure, it can be seen that P elements are distributed in epoxy matrix well, illustrate that terminal hydroxy group is phosphorous
Polyester has good compatibility with polyester, and it can not reunite with fine dispersion in epoxy matrix.This makes epoxy with it
Matrix obtains good mechanical performance and fire resistance is closely related.
Embodiment
With reference to embodiment so that the invention will be further described.It is necessarily pointed out that following examples can not
Be interpreted as limiting the scope of the invention, if the person skilled in the art in the field according to the invention described above content to this hair
It is bright to make some nonessential modifications and adaptations, still fall within the scope of the present invention.
The evaluation method of the present invention is as follows：
(1) intrinsic viscosity [η] of terminal hydroxy group phosphorous-containing polyester provided by the invention is 2, the 2- tetrachloroethanes with phenol/1,1
(1:1, v:V) it is solvent, is configured to the solution that concentration is 0.20g/dL, is obtained with dark type viscometer in 25 DEG C of tests.
(2) the number-average molecular weight Mn of terminal hydroxy group phosphor-containing flame-proof polyester provided by the invention is to be tested using gel chromatography GPC
Obtain；
(3) limited oxygen index provided by the invention is using HC-2C type limited oxygen indexs analyzer, according to ASTM
D2863-97 limited oxygen indexs (batten size：130×6.5×3mm3) method as defined in testing standard is respectively to pure sample and modification
Material carries out limited oxygen index (Limited oxygen index, LOI) test and obtained；
(4) vertical combustion grade provided by the invention is using CZF-2 types Vertical combustion instrument, vertical according to ASTMD3801
Burning (batten size：130×13×3mm3) method as defined in testing standard material modified fired to pure sample and vertically respectively
Test is burnt to obtain；
(5) unnotched impact strength tests (UnnotchedIzod used by impact strength data provided by the invention
Impact strength testing) it is the standard according to ASTM D256 in single armed Charpy impact tester (Sansi
ZBC1400-2 carried out on), batten size is 80 × 10 × 4mm3, environment temperature is 25 DEG C；
(6) used by tensile strength data provided by the invention extension test (Tensile testing) be according to
ASTM D638 standard is carried out on uniaxial tensile tester (Instron 5567), rate of extension 1mm/min, environment temperature
Spend for 25 DEG C, sample shape is 75 × 4 × 2mm3Dumbbell shape；
(7) crooked test (Flexural testing) that bending strength data provided by the invention use is according to ASTM
D790 standard is carried out on Instron1195 universal testing machines, span 32mm, loading speed 2mm/min, environment
Temperature is 25 DEG C, and sample shape is 80 × 10 × 4mm3Long strip type.
Embodiment 1
By 18.626g (0.10mol) '-biphenyl diphenol, 16.00g sodium hydroxides, 0.17g KIs and 250ml N, N-
Dimethylformamide is added in reaction vessel, the air led in nitrogen exclusion system, heating stirring, until solid all dissolves.
Under nitrogen protection, the chloro- 1- hexanols of 34.155g (0.25mol) 6- are slowly dropped in reaction system, are heated to reflux 24h, it is cold
But to room temperature.Reaction solution is poured into 2000ml beaker, add 1000ml distilled water, stir 1h, filtering；Add and steam again
Distilled water agitation and filtration, filter residue are cleaned repeatedly with distilled water, until filtrate is in neutrality.The filter residue finally obtained is placed under infrared lamp and done
It is dry, it is subsequently placed in 80 DEG C of vacuum drying oven and dries 24h, it is biphenyl dioxy hexanol to obtain white solid.
40.585g (0.105mol) biphenyl dioxy hexanol, 34.727g (0.100mol) DDP are added in reaction vessel, so
Afterwards under nitrogen protection, esterification 4h is stirred in 180 DEG C, adds 0.70ml butyl titanate toluene solutions (0.20gml-1), and solution is heated to 220 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h and obtains terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 8.60 × 103g·mol-1。
Embodiment 2
39.425g (0.102mol) biphenyl dioxy hexanol, 34.727g (0.100mol) DDP are added in reaction vessel, so
Afterwards under nitrogen protection, in 180 DEG C of stirrings, esterification 4h, 0.02ml butyl titanate toluene solutions (0.20gml is added-1), and solution is heated to 220 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h produces terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 1.20 × 104g·mol-1。
Embodiment 3
39.039g (0.101mol) biphenyl dioxy hexanol, 34.727g (0.100mol) DDP are added in reaction vessel, so
Afterwards under nitrogen protection, esterification 4h is stirred in 180 DEG C, adds 0.80ml butyl titanate toluene solutions (0.20gml-1), 220 DEG C are heated to afterwards, and low vacuum polycondensation 0.5h, high vacuum polycondensation 6h produces terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 2.80 × 104g·mol-1。
Embodiment 4
39.039g (0.101mol) biphenyl dioxy hexanol, 33.327g (0.100mol) DOPO-MA are added into reaction vessel
In, then under nitrogen protection, in 180 DEG C of stirrings, esterification 4h, add 0.80ml butyl titanate toluene solutions
(0.20g·ml-1), 220 DEG C are heated to afterwards, and low vacuum polycondensation 0.5h, high vacuum polycondensation 6h produces terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 1.50 × 104g·mol-1。
Embodiment 5
By 39.425g (0.102mol) biphenyl dioxy hexanol, 42.241g (0.100mol) 4,4'- (diphenylphosphoryl) hexichol
Ethyl formate, 0.20g zinc acetates and 0.80ml butyl titanate toluene solutions (0.20gml-1), add in reaction vessel, so
Afterwards under nitrogen protection, in 180 DEG C of stirrings, ester exchange reaction 4h, 230 DEG C, low vacuum polycondensation 0.5h are heated to afterwards, high vacuum
Polycondensation 6h produces terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 2.30 × 104g·mol-1。
Embodiment 6
By 39.425g (0.102mol) biphenyl dioxy hexanol, 21.420g (0.100mol) phosphenylic acid diethylester, 0.15g
Zinc acetate and 0.70ml butyl titanate toluene solutions (0.20gml-1), add in reaction vessel, then under nitrogen protection,
In 180 DEG C of stirrings, ester exchange reaction 4h, 210 DEG C are heated to afterwards, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h produces end hydroxyl
Base phosphorous-containing polyester.
The Mn of the polyester is 1.80 × 103g·mol-1。
Embodiment 7
By 39.039g (0.101mol) biphenyl dioxy hexanol, 21.420g (0.100mol) phosphenylic acid diethylester, 0.15g
Zinc acetate and 0.7ml butyl titanate toluene solutions (0.20gml-1), add in reaction vessel, then under nitrogen protection,
In 180 DEG C of stirrings, ester exchange reaction 4h, 210 DEG C are heated to afterwards, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h produces end hydroxyl
Base phosphorous-containing polyester.
The Mn of the polyester is 2.00 × 103g·mol-1。
Embodiment 8
By 38.845g (0.1005mol) biphenyl dioxy hexanol, 21.420g (0.100mol) phosphenylic acid diethylester,
0.15g zinc acetates and 0.7ml butyl titanate toluene solutions (0.20gml-1), add in reaction vessel, then protected in nitrogen
Under shield, ester exchange reaction 4h is stirred in 180 DEG C, is heated to 220 DEG C afterwards, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h is produced
Terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 2.50 × 103g·mol-1。
Embodiment 9
By 38.845g (0.1005mol) biphenyl dioxy hexanol, 13.810g (0.100mol) diethyl phosphite, 0.10g
Zinc acetate and 0.50ml butyl titanate toluene solutions (0.20gml-1), add in reaction vessel, then under nitrogen protection,
Ester exchange reaction 4h is stirred in 170 DEG C, is heated to 220 DEG C afterwards, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h produces terminal hydroxy group
Phosphorous-containing polyester.
The Mn of the polyester is 1.90 × 103g·mol-1。
Embodiment 10
By 38.845g (0.1005mol) biphenyl dioxy hexanol, 15.213g (0.100mol) methyl acid phosphate diethylester,
0.10g zinc acetates and 0.70ml butyl titanate toluene solutions (0.20gml-1), add in reaction vessel, then protected in nitrogen
Under shield, ester exchange reaction 4h is stirred in 180 DEG C, is heated to 210 DEG C afterwards, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h is produced
Terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 2.50 × 103g·mol-1。
Embodiment 11
By 38.845g (0.1005mol) biphenyl dioxy hexanol, 22.822g (0.100mol) benzyl diethyl phosphate,
0.15g zinc acetates and 0.70ml butyl titanate toluene solutions (0.20gml-1), add in reaction vessel, then protected in nitrogen
Under shield, ester exchange reaction 4h is stirred in 180 DEG C, is heated to 200 DEG C afterwards, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h is produced
Terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 3.60 × 103g·mol-1。
Embodiment 12
By 51.070g (0.50mol) phenylacetylene, diethyl phosphite 82.860g (0.60mol), cuprous iodide 9.50g,
Triethylamine 15.00g, 1500ml DMSO, add in reaction vessel, under air atmosphere, stirring reaction 48h at 55 DEG C of constant temperature.Cooling
To room temperature, about 1500ml water is added in reaction solution, is extracted with ethyl acetate, merge organic phase, with saturated common salt water washing 3 times,
Revolving removes ethyl acetate, uses column chromatography grease, eluent PE:EA=1：2, obtain chartreuse oily produce
Thing.
By 39.039g (0.101mol) biphenyl dioxy hexanol, 23.822g (0.100mol) phenylacetylene base diethyl phosphate,
0.15g zinc acetates and 0.70ml butyl titanate toluene solutions (0.20gml-1), add in reaction vessel, then protected in nitrogen
Under shield, ester exchange reaction 4h is stirred in 180 DEG C, is heated to 210 DEG C afterwards, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h is produced
Terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 2.80 × 103g·mol-1。
Embodiment 13
By 34.601g (0.20mol) p bromophenol, 12.00g sodium hydroxides, in 1.94g KI reaction vessels, add
240ml DMAc, the air led in nitrogen exclusion system, heating stirring, until solid all dissolves., will under nitrogen protection
Chloro- 1 hexanols of 40.986g (0.30mol) 6- are slowly dropped in reaction system, are opened and are stirred and be warming up to 166 DEG C, treat that temperature reaches
1- chloropropyl alcohols are slowly added dropwise during to 120 DEG C, afterwards back flow reaction 12h.24h is heated to reflux, is cooled to room temperature.After reaction terminates,
Filter, filtrate is poured into 500ml beakers, add appropriate 5% NaOH solution, dichloromethane extraction.Organic phase distilled water
Wash repeatedly, until filtrate is in neutrality.Be spin-dried for organic phase, you can obtain yellow oily liquid product 6- (4 '-bromophenyl epoxide)-
1- hexanols.
27.317g (0.10mol) 6- (4 '-bromo- phenyl epoxide) -1- hexanols, 220ml triethylamines, 130mlDBU are added
In reaction vessel, nitrogen protection is lower to add 0.80g cuprous iodides and 0.93g triphenylphosphine palladium chlorides.Added by syringe
9.50ml trimethylsilyl acetylene and 0.90ml deionized waters, 24h is reacted at 70 DEG C.Room temperature is cooled to, filters, filtrate is poured into
In the 2L beakers equipped with 1000ml distilled water, 2h is stirred, stands 12h afterwards.Solid is separated out, is filtered, gained filter residue ammoniacal liquor
Washing 2 times, the multiple washing of distilled water afterwards is until filtrate is in neutrality.Last solid re-crystallizing in ethyl acetate, obtains yellow and consolidates
Body product 4,4 '-bis- (6- hydroxyls hexyloxy) tolans.
By 20.733g (0.0505mol) 4,4 '-bis- (6- hydroxyls hexyloxies) tolans, 17.364g (0.05mol)
DDP, 0.07g zinc acetate, 0.11mg antimony oxides are added in reaction vessel.Then under nitrogen protection, ester is stirred in 180 DEG C
Exchange reaction 4h, 210 DEG C is heated to afterwards, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h produces terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 2.20 × 104g·mol-1。
Embodiment 14
By 20.733g (0.0505mol) 4,4 '-bis- (6- hydroxyls hexyloxies) tolans, 10.710g (0.05mol) benzene
Base diethyl phosphate, 0.10g zinc acetates and 0.70ml butyl titanate toluene solutions (0.20gml-1), add reaction vessel
In.Then under nitrogen protection, ester exchange reaction 4h is stirred in 180 DEG C, is heated to 210 DEG C, low vacuum polycondensation 0.5h afterwards, height
Vacuum polycondensation 6h produces terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 2.60 × 104g·mol-1。
Embodiment 15
By 20.221g (0.10mol) 4,4'- dihydroxy diphenyl ethers, 16.00g sodium hydroxides, 0.17g KIs and
250ml DMF is added in reaction vessel, the air led in nitrogen exclusion system, heating stirring, until solid
Body all dissolves.Under nitrogen protection, the chloro- 1- hexanols of 34.155g (0.25mol) 6- are slowly dropped in reaction system, added
Heat backflow 24h, is cooled to room temperature.Reaction solution is poured into 2000ml beaker, add 1000ml distilled water, stir 1h, mistake
Filter；Distilled water agitation and filtration is added again, and filter residue is cleaned repeatedly with distilled water, until filtrate is in neutrality.The filter residue finally obtained
Be placed under infrared lamp and dry, be subsequently placed in 80 DEG C of vacuum drying oven and dry 24h, obtain pale solid be 4,4 '-bis- (6- hydroxyls
Hexyloxy) diphenyl ether.
40.455g (0.101mol) 4,4 '-bis- (6- hydroxyls hexyloxies) diphenyl ether, 34.727g (0.100mol) DDP are added
Enter in reaction vessel, then under nitrogen protection, stir esterification 4h in 180 DEG C, add 1.00ml butyl titanate toluene
Solution (0.20gml-1), and solution is heated to 220 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h and obtains terminal hydroxy group
Phosphorous-containing polyester.
The Mn of the polyester is 2.80 × 104g·mol-1。
Embodiment 16
By 20.023g (0.100mol) Bisphenol F, 16.00g sodium hydroxides, 0.17g KIs and 250ml N, N- bis-
NMF is added in reaction vessel, the air led in nitrogen exclusion system, heating stirring, until solid all dissolves.
Under nitrogen protection, the chloro- 1- hexanols of 34.155g (0.25mol) 6- are slowly dropped in reaction system, are heated to reflux 24h, cooled down
To room temperature.Reaction solution is poured into 2000ml beaker, add 1000ml distilled water, stir 1h, filtering；Distillation is added again
Water agitation and filtration, filter residue are cleaned repeatedly with distilled water, until filtrate is in neutrality.The filter residue finally obtained is placed under infrared lamp and done
It is dry, be subsequently placed in 80 DEG C of vacuum drying oven and dry 24h, obtain white solid be 4,4 '-bis- (6- hydroxyls hexyloxy) diphenyl-methanes.
By 40.255g (0.1005mol) 4,4 '-bis- (6- hydroxyls hexyloxies) diphenyl-methane, 34.727g (0.100mol)
DDP is added in reaction vessel, then under nitrogen protection, is stirred esterification 4h in 180 DEG C, is added 1.00ml butyl titanates
Toluene solution (0.20gml-1), and solution is heated to 220 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h and held
Hydroxyl phosphorous-containing polyester.
The Mn of the polyester is 2.50 × 104g·mol-1。
Embodiment 17
By 22.829g (0.10mol) bisphenol-A, 16.00g sodium hydroxides, 0.17g KIs and 250ml N, N- diformazans
Base formamide is added in reaction vessel, the air led in nitrogen exclusion system, heating stirring, until solid all dissolves.In nitrogen
Under gas shielded, the chloro- 1- hexanols of 34.155g (0.25mol) 6- are slowly dropped in reaction system, 24h is heated to reflux, is cooled to
Room temperature.Reaction solution is poured into 2000ml beaker, add 1000ml distilled water, stir 1h, filtering；Distilled water is added again
Agitation and filtration, filter residue are cleaned repeatedly with distilled water, until filtrate is in neutrality.The filter residue finally obtained is placed under infrared lamp and dried,
Be subsequently placed in 80 DEG C of vacuum drying oven and dry 24h, obtain white solid be 4,4 '-bis- (6- hydroxyls hexyloxy) diphenyl propanes.
By 43.074g (0.1005mol) 4,4 '-bis- (6- hydroxyls hexyloxies) diphenyl propane, 34.727g (0.100mol)
DDP is added in reaction vessel, then under nitrogen protection, is stirred esterification 4h in 180 DEG C, is added 1.00ml butyl titanates
Toluene solution (0.20gml-1), and solution is heated to 220 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h and held
Hydroxyl phosphorous-containing polyester.
The Mn of the polyester is 2.8 × 104g·mol-1。
Embodiment 18
By 25.027g (0.10mol) bisphenol S, 16.00g sodium hydroxides, 0.17g KIs and 250ml N, N- diformazans
Base formamide is added in reaction vessel, the air led in nitrogen exclusion system, heating stirring, until solid all dissolves.In nitrogen
Under gas shielded, the chloro- 1- hexanols of 34.155g (0.25mol) 6- are slowly dropped in reaction system, 24h is heated to reflux, is cooled to
Room temperature.Reaction solution is poured into 2000ml beaker, add 1000ml distilled water, stir 1h, filtering；Distilled water is added again
Agitation and filtration, filter residue are cleaned repeatedly with distilled water, until filtrate is in neutrality.The filter residue finally obtained is placed under infrared lamp and dried,
Be subsequently placed in 80 DEG C of vacuum drying oven and dry 24h, obtain white solid be 4,4 '-bis- (6- hydroxyls hexyloxy) diphenyl sulphone (DPS)s.
By 45.284g (0.1005mol) 4,4 '-bis- (6- hydroxyls hexyloxies) diphenyl sulphone (DPS), 34.727g (0.100mol) DDP
Add in reaction vessel, then under nitrogen protection, stir esterification 4h in 180 DEG C, it is molten to add 1ml butyl titanate toluene
Liquid (0.20gml-1), and it is to obtain terminal hydroxy group to contain that solution is heated into 220 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h
Phosphorus polyester.
The Mn of the polyester is 2.10 × 104g·mol-1。
Embodiment 19
By 35.041g (0.10mol) bisphenol fluorene, 16g.00 sodium hydroxides, 0.17g KIs and 250ml N, N- bis-
NMF is added in reaction vessel, the air led in nitrogen exclusion system, heating stirring, until solid all dissolves.
Under nitrogen protection, the chloro- 1- hexanols of 34.155g (0.25mol) 6- are slowly dropped in reaction system, are heated to reflux 24h, cooled down
To room temperature.Reaction solution is poured into 2000ml beaker, add 1000ml distilled water, stir 1h, filtering；Distillation is added again
Water agitation and filtration, filter residue are cleaned repeatedly with distilled water, until filtrate is in neutrality.The filter residue finally obtained is placed under infrared lamp and done
It is dry, be subsequently placed in 80 DEG C of vacuum drying oven and dry 24h, obtain white solid be 4,4 '-bis- (6- hydroxyls hexyloxy) diphenylfluorenes.
By 55.348g (0.1005mol) 4,4 '-bis- (6- hydroxyls hexyloxies) diphenylfluorene, 34.727g (0.100mol)
DDP is added in reaction vessel, then under nitrogen protection, is stirred esterification 4h in 180 DEG C, is added 1.20ml butyl titanates
Toluene solution (0.20gml-1), and solution is heated to 220 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h and held
Hydroxyl phosphorous-containing polyester.
The Mn of the polyester is 3.50 × 104g·mol-1。
Embodiment 20
By 18.621g (0.10mol) '-biphenyl diphenol, 16.00g sodium hydroxides, 0.17g KIs and 250ml N, N-
Dimethylformamide is added in reaction vessel, the air led in nitrogen exclusion system, heating stirring, until solid all dissolves.
Under nitrogen protection, 23.635g (0.25mol) trimethylene chlorohydrin is slowly dropped in reaction system, is heated to reflux 24h, it is cold
But to room temperature.Reaction solution is poured into 2000ml beaker, add 1000ml distilled water, stir 1h, filtering；Add and steam again
Distilled water agitation and filtration, filter residue are cleaned repeatedly with distilled water, until filtrate is in neutrality.The filter residue finally obtained is placed under infrared lamp and done
It is dry, it is subsequently placed in 80 DEG C of vacuum drying oven and dries 24h, it is biphenyl dioxy propyl alcohol to obtain white solid.
30.538g (0.101mol) biphenyl dioxy propyl alcohol, 34.727g (0.100mol) DDP are added in reaction vessel, so
Afterwards under nitrogen protection, esterification 4h is stirred in 210 DEG C, adds 0.60ml butyl titanate toluene solutions (0.20gml-1), and solution is heated to 240 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h and obtains terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 1.80 × 104g·mol-1。
Embodiment 21
By 18.621g (0.10mol) '-biphenyl diphenol, 16.00g sodium hydroxides, 0.17g KIs and 250ml N, N-
Dimethylformamide is added in reaction vessel, the air led in nitrogen exclusion system, heating stirring, until solid all dissolves.
Under nitrogen protection, the chloro- 1- octanols of 41.168g (0.25mol) 8- are slowly dropped in reaction system, are heated to reflux 24h, it is cold
But to room temperature.Reaction solution is poured into 2000ml beaker, add 1000ml distilled water, stir 1h, filtering；Add and steam again
Distilled water agitation and filtration, filter residue are cleaned repeatedly with distilled water, until filtrate is in neutrality.The filter residue finally obtained is placed under infrared lamp and done
It is dry, it is subsequently placed in 80 DEG C of vacuum drying oven and dries 24h, it is biphenyl dioxy octanol to obtain white solid.
44.706g (0.101mol) biphenyl dioxy octanol, 34.727g (0.100mol) DDP are added in reaction vessel, so
Afterwards under nitrogen protection, esterification 4h is stirred in 180 DEG C, adds 0.80ml butyl titanate toluene solutions (0.20gml-1), and solution is heated to 200 DEG C, low vacuum polycondensation 0.5h, high vacuum polycondensation 6h and obtains terminal hydroxy group phosphorous-containing polyester.
The Mn of the polyester is 3.80 × 104g·mol-1。
Embodiment 22-26
5 parts by weight terminal hydroxy group phosphorous-containing polyesters prepared by embodiment 1,2,3,4,5 add the bisphenol-A type ring equipped with 80 parts by weight
In oxygen tree fat E51 container, heating stirring to polyester is completely dissolved.By the curing agent of the complete melting of mixture and 20 parts by weight
DDM is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and mould is put into
Solidified in vulcanizing press, solidified 2 hours at 80 DEG C, solidified 2 hours at 160 DEG C, then solidify 2 at 180 DEG C
Hour.The correlated performance of the halogen-free flameproof activeness and quietness epoxy composite material of preparation see the table below 1.
Table 1
Embodiment 27-35
The terminal hydroxy group phosphorous-containing polyester of different weight part (1-30) prepared by embodiment 2 adds the bis-phenol equipped with 80 parts by weight
In A type epoxy resin E51 container, heating stirring to polyester is completely dissolved.By the complete melting of mixture and 20 parts by weight
Curing agent DDM is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and by mould
Tool, which is put into vulcanizing press, to be solidified, and is solidified 2 hours at 80 DEG C, is solidified 2 hours at 160 DEG C, then at 180 DEG C
Solidification 2 hours.The correlated performance of the halogen-free flameproof activeness and quietness epoxy composite material of preparation see the table below 2.
Table 2
Embodiment 36-39
The terminal hydroxy group phosphorous-containing polyester of 15 parts by weight prepared by embodiment 8,9,10,11 adds the bis-phenol equipped with 80 parts by weight
In A type epoxy resin E51 container, heating stirring to polyester is completely dissolved.By the complete melting of mixture and 20 parts by weight
Curing agent DDM is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and by mould
Tool, which is put into vulcanizing press, to be solidified, and 80 DEG C solidify 2 hours, and 160 DEG C solidify 2 hours, then solidify 2 hours at 180 DEG C.
The correlated performance of the halogen-free flameproof activeness and quietness epoxy composite material of preparation see the table below 3.
Table 3
Embodiment 40-42
The terminal hydroxy group phosphorous-containing polyester of 10 parts by weight prepared by embodiment 12,13,14 adds the bisphenol-A equipped with 80 parts by weight
In type epoxy resin E51 container, heating stirring to polyester is completely dissolved.By consolidating for mixture and the complete melting of 20 parts by weight
Agent DDM is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and by mould
It is put into vulcanizing press and is solidified, 80 DEG C solidifies 2 hours, and 160 DEG C solidify 2 hours, then solidify 2 hours at 180 DEG C.System
The correlated performance of standby halogen-free flameproof activeness and quietness epoxy composite material see the table below 4.
Table 4
Embodiment 43-47
The terminal hydroxy group phosphorous-containing polyester of 15 parts by weight prepared by embodiment 15,16,17,18,19 adds and 80 parts by weight is housed
Bisphenol A type epoxy resin E51 container in, heating stirring to polyester is completely dissolved.By the complete of mixture and 20 parts by weight
The curing agent DDM of melting is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould,
And mould is put into vulcanizing press and solidified, 80 DEG C solidify 2 hours, and 160 DEG C solidify 2 hours, then in 180 DEG C of solidifications
2 hours.The correlated performance of the halogen-free flameproof activeness and quietness epoxy composite material of preparation see the table below 5.
Table 5
Embodiment 48-50
The terminal hydroxy group phosphorous-containing polyester of 12 parts by weight prepared by embodiment 2,8,13 adds the bisphenol A-type equipped with 69 parts by weight
In epoxy resin E51 container, heating stirring to polyester is completely dissolved.By the solidification of the complete melting of mixture and 31 parts by weight
Agent DDS is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and mould is put
Enter in vulcanizing press and solidified, 100 DEG C solidify 2 hours, and 180 DEG C solidify 2 hours, then solidify 2 hours at 220 DEG C.System
The correlated performance of standby halogen-free flameproof activeness and quietness epoxy composite material see the table below 6.
Table 6
Embodiment 51-55
The terminal hydroxy group phosphorous-containing polyester of 2.5 parts by weight prepared by embodiment 15,16,17,18,19 adds and 80 parts by weight is housed
Bisphenol A type epoxy resin E51 container in, heating stirring to polyester is completely dissolved.By the complete of mixture and 20 parts by weight
The curing agent DDM of melting is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould,
And mould is put into vulcanizing press and solidified, 80 DEG C solidify 2 hours, and 160 DEG C solidify 2 hours, then in 180 DEG C of solidifications
2 hours.The correlated performance of the halogen-free flameproof activeness and quietness epoxy composite material of preparation see the table below 7.
Table 7
Embodiment 56-60
The terminal hydroxy group phosphorous-containing polyester of 15 parts by weight prepared by embodiment 15,16,17,18,19 adds and 69 parts by weight is housed
Bisphenol A type epoxy resin E51 container in, heating stirring to polyester is completely dissolved.By the complete of mixture and 31 parts by weight
The curing agent DDS of melting is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould,
And mould is put into vulcanizing press and solidified, 100 DEG C solidify 2 hours, and 180 DEG C solidify 2 hours, then solid at 220 DEG C
Change 2 hours.The correlated performance of the halogen-free flameproof activeness and quietness epoxy composite material of preparation see the table below 8.
Table 8
Embodiment 61-62
The terminal hydroxy group phosphorous-containing polyester of 15 parts by weight prepared by embodiment 20,21 adds the bisphenol A-type equipped with 80 parts by weight
In epoxy resin E51 container, heating stirring to polyester is completely dissolved.By the solidification of the complete melting of mixture and 20 parts by weight
Agent DDM is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and mould is put
Enter in vulcanizing press and solidified, 80 DEG C solidify 2 hours, and 160 DEG C solidify 2 hours, then solidify 2 hours at 180 DEG C.Prepare
The correlated performance of halogen-free flameproof activeness and quietness epoxy composite material see the table below 9.
Table 9
Embodiment 63-71
The terminal hydroxy group phosphorous-containing polyester of different weight part (1-30) prepared by embodiment 2 adds the bis-phenol equipped with 90 parts by weight
In A type epoxy resin E44 container, heating stirring to polyester is completely dissolved.By the complete melting of mixture and 10 parts by weight
Curing agent DETA is uniformly mixed.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and by mould
Tool, which is put into vulcanizing press, to be solidified, and is solidified 2 hours at 80 DEG C, is solidified 2 hours at 160 DEG C, then at 180 DEG C
Solidification 2 hours.The correlated performance of the halogen-free flameproof activeness and quietness epoxy composite material of preparation see the table below 10.
Table 10
Embodiment 72-76
The terminal hydroxy group phosphorous-containing polyester of 15 parts by weight prepared by embodiment 1,2,3,4,5 adds the bis-phenol equipped with 60 parts by weight
In A type epoxy resin E51 container, heating stirring to polyester is completely dissolved.Mixture and the methyl tetrahydrochysene of 40 parts by weight is adjacent
Benzene diformazan phthalic anhydride (MeTHPA) is uniformly mixed, and adds curing accelerator [2,4,5- tri- (dimethylamino methyls) of 1 parts by weight
Phenol.De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and mould is put into vulcanizing press
Solidified, solidified 2 hours at 100 DEG C, solidified at 120 DEG C 2 hours, then solidify 6 hours at 160 DEG C.Prepare
The correlated performance of halogen-free flameproof activeness and quietness epoxy composite material see the table below 11.
Table 11
Comparative example 1
The 80g bisphenol A type epoxy resins E51 and 20g DDM melted completely are mixed and stirred for, after fully mixing, vacuum is removed
Bubble, is poured the mixture into warmed-up polytetrafluoro mould afterwards, and mould is put into vulcanizing press and solidified, 80 DEG C
Solidification 2 hours, 160 DEG C solidify 2 hours, then solidify 2 hours at 180 DEG C.The LOI of gained epoxy resin cured product is
26.5%, UL-94 (3.2mm) are NR levels, and unnotched impact strength is 12.0kJ m-2, tensile strength 70MPa, bending strength
For 113MPa.
Comparative example 2
The 69g bisphenol A type epoxy resins E51 and 20g DDM melted completely are mixed and stirred for, after fully mixing, vacuum is removed
Bubble, is poured the mixture into warmed-up polytetrafluoro mould afterwards, and mould is put into vulcanizing press and solidified, and 100
DEG C solidification 2 hours, 180 DEG C solidify 2 hours, then 220 DEG C solidify 2 hours.The LOI of gained epoxy resin cured product is
24.5%, UL-94 (3.2mm) are NR levels, and unnotched impact strength is 13.4kJ m-2, tensile strength 65MPa, bending strength
For 110MPa.
Comparative example 3
The 90g bisphenol A type epoxy resins E44 and 10g DETA melted completely are mixed and stirred for, after fully mixing, vacuum
De-bubble, pour the mixture into afterwards in warmed-up polytetrafluoro mould, and mould is put into vulcanizing press and solidified,
Cold curing 6 hours, 180 DEG C solidify 2 hours.The LOI of gained epoxy resin cured product is that 22.0%, UL-94 (3.2mm) is NR
Level, unnotched impact strength 11.2kJm-2, tensile strength 63MPa, bending strength 107MPa.
Comparative example 4
By the bisphenol A type epoxy resin E51 of 60 parts by weight and the methyl tetrahydrochysene O-phthalic phthalic anhydride of 40 parts by weight
(MeTHPA) it is uniformly mixed, adds (dimethylamino methyl) phenol (DMP- of curing accelerator 2,4,5- tri- of 1 parts by weight
30).De-bubble is vacuumized, is poured the mixture into afterwards in warmed-up polytetrafluoro mould, and mould is put into vulcanizing press
Solidified, solidified 2 hours at 100 DEG C, solidified at 120 DEG C 2 hours, then solidify 6 hours at 160 DEG C.Gained ring
The LOI of oxygen resin cured matter is that 20.0%, UL-94 (3.2mm) is NR levels, and unnotched impact strength is 9.3kJ m-2, stretching is by force
Spend for 61MPa, bending strength 110MPa.
Claims (10)
1. a kind of terminal hydroxy group phosphorous-containing polyester, it is made up of following I, II or I, III construction unit represented：
In formula, R1Represent-,-CH2- ,-O-,Any of；n
For 2-8 integer；
In formula, R2For any of H atom, methyl, methylene, phenyl, benzyl or phenylacetylene base.
A kind of 2. terminal hydroxy group phosphorous-containing polyester as claimed in claim 1, it is characterised in that：Described structural units I monomer and knot
Structure unit II monomer feeds intake by a mole equivalent proportion 1.005-1.05, and obtained phosphorous-containing polyester intrinsic viscosity [η] is 0.46-
0.98dL/g, number-average molecular weight [Mn] are 5000g/mol-50000g/mol；Described structural units I monomer and construction unit III
Monomer feeds intake by a mole equivalent proportion 1.005-1.05, and the intrinsic viscosity [η] of obtained phosphorous-containing polyester is 0.25-0.48dL/g, number
Average molecular weight [Mn] is 1800g/mol-8000g/mol, and the phosphorous-containing polyester being prepared is hydroxy-end capped.
A kind of 3. preparation method of terminal hydroxy group phosphorous-containing polyester as claimed in claim 1 or 2, it is characterised in that：Described method
It is by the dihydric alcohol containing methylene number 2-8 and binary acid or its carboxylate, is carried out using direct esterification or ester-interchange method
After esterification, catalyst is added, is obtained by polycondensation reaction.
4. the preparation method of terminal hydroxy group phosphorous-containing polyester as claimed in claim 3, it is characterised in that：Described dihydric alcohol is following
Any of structure, n are 2-8 integer：
Described binary acid or its carboxylate are any of following structure：
5. the preparation method of terminal hydroxy group phosphorous-containing polyester as claimed in claim 3, it is characterised in that：Described polycondensation of polyester catalysis
Agent is at least one of zinc acetate, manganese acetate, cobalt acetate, antimony oxide, antimony glycol or titanate esters.
A kind of 6. side that halogen-free flameproof activeness and quietness epoxy resin is prepared using terminal hydroxy group phosphorous-containing polyester as claimed in claim 1
Method, it is characterised in that：Comprise the following steps：Described terminal hydroxy group phosphorous-containing polyester is mixed with epoxy resin, heating stirring is to molten
Mixture, is well mixed, pours into mould and solidify after froth in vacuum by solution with curing agent afterwards.
7. the method that terminal hydroxy group phosphorous-containing polyester as claimed in claim 6 prepares halogen-free flameproof activeness and quietness epoxy resin, it is special
Sign is：By weight, the described terminal hydroxy group phosphorous-containing polyester of addition is 1-30 parts, and described epoxy resin is 60-90 parts,
Described curing agent is 10-40 parts.
8. the side that halogen-free flameproof activeness and quietness epoxy resin is prepared using terminal hydroxy group phosphorous-containing polyester as claimed in claims 6 or 7
Method, it is characterised in that：The epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, more phenolic glycidol ethers
Epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin,
Any of epoxidation of olefins compound, heterocyclic-type epoxy resin and mixed type epoxy resin are several.
9. the side that halogen-free flameproof activeness and quietness epoxy resin is prepared using terminal hydroxy group phosphorous-containing polyester as claimed in claims 6 or 7
Method, it is characterised in that：Described curing agent is aliphatic polyol amine type curing agent, cycloaliphatic polyols amine type curing agent, fragrant amine type are consolidated
Agent, acid anhydride type curing agent, polyamide-type hardener, cyanogen amine curing agent, imidazole curing agent and modified amine curing agent
Any of or it is several.
A kind of 10. halogen-free flameproof activeness and quietness epoxy composite material, it is characterised in that：Described composite is by described by weight
Measure the hydroxy-end capped phosphorous-containing polyester of part meter 1-30 parts, 60-90 parts epoxy resin, 10-40 parts curing agent composition, tensile strength 45-
95MPa, unnotched impact strength 10-45KJ/m2, bending strength 80-168MPa, limited oxygen index 22.0-43.5%,
Vertical combustion grade is V-1-V-0 levels.
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| CN201710858351.XA CN107739433B (en) | 2017-09-21 | 2017-09-21 | Hydroxyl-terminated phosphorus-containing polyester, preparation method and application thereof, and halogen-free flame-retardant reinforced toughened epoxy composite material |
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| CN201710858351.XA CN107739433B (en) | 2017-09-21 | 2017-09-21 | Hydroxyl-terminated phosphorus-containing polyester, preparation method and application thereof, and halogen-free flame-retardant reinforced toughened epoxy composite material |
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| CN107739433A true CN107739433A (en) | 2018-02-27 |
| CN107739433B CN107739433B (en) | 2020-02-07 |
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| CN109734899A (en) * | 2018-11-26 | 2019-05-10 | 东华大学 | A kind of copoly type function nylon 6/poly closes object and preparation method thereof |
| CN110591053A (en) * | 2019-10-09 | 2019-12-20 | 厦门珉瑶贸易有限公司 | Heat insulation material of hard polyurethane foam |
| CN113045741A (en) * | 2019-12-26 | 2021-06-29 | 洛阳尖端技术研究院 | Phosphorus-containing carboxyl-terminated hyperbranched polyester, preparation method thereof, phosphorus-containing hyperbranched epoxy resin, preparation method thereof and application thereof |
| CN113174050A (en) * | 2021-05-08 | 2021-07-27 | 株洲市九华新材料涂装实业有限公司 | Elastic epoxy resin and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109734899A (en) * | 2018-11-26 | 2019-05-10 | 东华大学 | A kind of copoly type function nylon 6/poly closes object and preparation method thereof |
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| CN113174050A (en) * | 2021-05-08 | 2021-07-27 | 株洲市九华新材料涂装实业有限公司 | Elastic epoxy resin and application thereof |
| CN113174050B (en) * | 2021-05-08 | 2022-06-07 | 株洲市九华新材料涂装实业有限公司 | Elastic epoxy resin and application thereof |
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| CN107739433B (en) | 2020-02-07 |
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