CN106832302A - A kind of preparation method of hydroxyl phosphonitrilic resin - Google Patents
A kind of preparation method of hydroxyl phosphonitrilic resin Download PDFInfo
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- CN106832302A CN106832302A CN201710081344.3A CN201710081344A CN106832302A CN 106832302 A CN106832302 A CN 106832302A CN 201710081344 A CN201710081344 A CN 201710081344A CN 106832302 A CN106832302 A CN 106832302A
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- phosphonitrilic
- tetrachloroethanes
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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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
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- 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
- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
- C09D185/02—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers containing phosphorus
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Abstract
The present invention discloses a kind of preparation method of hydroxyl phosphonitrilic resin, belongs to a kind of new phosphazene compound of chemical industry and polymeric material field and preparation method thereof.The compound generates hydroxyl phosphonitrilic chloride tripolymer by hydroxylamine hydrochloride, phosphorus trichloride, chlorine reaction, then is worth with hydroquinones polycondensation reaction.Obtained hydroxyl phosphonitrilic resin of the invention, can rise with temperature and voluntarily solidify, and largely reduce the solidification difficulty and solidification cost of conventional phosphonitrilic resin, and application of the resin in the fields such as coating is provided a great convenience.
Description
Technical field
The present invention relates to chemical industry and polymeric material field, particularly a kind of preparation method of new phosphazene compound.
Background technology
Phosphonitrilic resin is that skeleton is alternately arranged by phosphorus nitrogen list double bond, and side base is by the organic high score of element that organic group is constituted
Son, mainly includes ring-type and the major class of linear phosphonitrilic resin two, and cyclic phosphazene resin applies more in terms of heat-resisting and fire-retardant composite, and
The application of linear phosphonitrilic resin is just more extensive, and the diversity of phosphonitrilic resin structure causes the multifunctionality of material, side chain it is each
Planting organic substituents assigns phosphorus eyeball polymer novel excellent characteristic, such as water-fast, solvent resistant, resistance to oils and chemicals, and resistance to
High temperature, low temperature and do not burn.
The preparation method of phosphonitrilic resin mainly includes：
1. linear phosphonitrilic resin is directly synthesized by ring phosphonitrile, such direct polymerization method mainly includes：Polymerisation in bulk and solvent are poly-
Close two classes.Polymerisation in bulk can be divided into again：Melting polymerisation in bulk and catalytic fusion polymerisation in bulk.Melting bulk polymerization belongs to sun
Ionic polymerization, its reaction condition is usually to carry out ring-opening polymerisation in the vacuum tube of isolation air and moisture, and temperature exists
250 DEG C or so, high conversion can not be simply pursued during reaction, can otherwise form cross-linking agent.The advantage of the method is obtained
Molecular weight of product is higher, and product is easy to and reactants separate, thus is widely used by laboratory and industry.Shortcoming is exactly anti-
Should be using the raw material of high-purity, reaction temperature very high and reaction time more long.
Another synthetic method of phosphonitrilic resin is the solvent polymerization method of ring phosphonitrile, and its ring-opening reaction is catalyzed with boron chloride
Agent, is carried out in high boiling solvent.Compared with the polymerisation in bulk of phosphonitrilic resin, the time shortens the method, temperature is reduced, is difficult shape
Improved into gel, conversion ratio, and the molecular weight distribution of polymerizate is narrower.But, the product point obtained currently with this method
Son amount is also relatively low, and more strict to the control requirement of polymerization temperature.
2. by polydichlorophosphazenes substitution reaction synthesizing linear phosphonitrilic resin
The synthetic method for preparing the poly- phosphorus eyeball with different substituents mainly has two kinds:One is to make poly- dichloro phosphorus eyeball and two kinds of differences
Nucleopilic reagent is reacted;Two is that substep replaces under certain condition, produces the phosphonitrilic resin with different substituents.
3. linear phosphonitrilic resin is prepared by ring phosphazene derivative
Derivative after one or more chlorine atoms on hexachlorocyclotriph,sphazene are replaced by other organic groups can also enter
Row ring-opening polymerisation.Experiment shows, organic group replaces the open loop of ring phosphonitrile to be relatively difficult, and partially substituted ring phosphonitrile entirely
Ring-opening polymerisation be easier realize.And after polymerization, its remaining halogen atom remains to be alkoxylated compound, aryloxy group
The organic nucleophiles such as compound, amine and organo-metallic compound are replaced,
4. it is directly synthesized linear phosphonitrilic resin from small molecule
Direct polymerization can also obtain linear phosphonitrilic resin to small molecule monomer under certain condition.
In existing phosphonitrilic resin preparation method, see by making the same alkoxy of substitution base, phenoxy group with terminal hydroxy group etc.
Mixing substitution polydichlorophosphazenes, prepare the report of crosslinkable phosphonitrile elastomer, there is not yet using hydroxylamine hydrochloride and tri-chlorination
Phosphorus, chlorine reaction directly generate hydroxyl phosphonitrilic chloride tripolymer, and then synthesize a kind of report of hydroxyl phosphonitrilic resin.This hair
The bright hydroxyl phosphonitrilic resin for obtaining, can rise with temperature and voluntarily solidify, and largely reduce consolidating for conventional phosphonitrilic resin
Change difficulty and solidification cost, application of the resin in the fields such as coating is provided a great convenience.
The content of the invention
It is an object of the invention to provide one kind hydroxyl is directly generated using hydroxylamine hydrochloride and phosphorus trichloride, chlorine reaction
Phosphonitrilic chloride tripolymer, and then synthesize a kind of preparation method of hydroxyl phosphonitrilic resin, the method has reaction temperature relatively
The characteristics of low, reaction time is relatively short, yield is higher, hydroxyl phosphonitrilic resin prepared by the present invention has with temperature simultaneously
Rise the characteristics of voluntarily solidifying.
The technical scheme is that：A kind of preparation method of hydroxyl phosphonitrilic resin, its step：1. by raw material hydrochloric acid hydroxyl
Amine, phosphorus trichloride, tetrachloroethanes, pyridine and waterless cobaltous chloride are with weight ratio as hydroxylamine hydrochloride: phosphorus trichloride: tetrachloroethanes: pyrrole
Pyridine: cobalt chloride=100: in 200~400: 500~800: 4~50: 2~20 ratio input reactor, it is three to be passed through addition
The chlorine of the 30~60% of phosphorus chloride weight, starts stirring, is heated to 70~150 DEG C, flows back 5~15 hours, cold after the completion of reaction
But to 60~80 DEG C, filtering removes unreacted cobalt chloride, then again vacuum distillation remove respectively unreacted phosphorus trichloride,
Pyridine and tetrachloroethanes, after adding the solid that obtains of petroleum ether dissolution, be weight percentage with concentration 5~10% dilute sulfuric acid dip
Wash, stir, standing, taking oil phase, vacuum distillation removing petroleum ether obtains faint yellow hydroxyl phosphonitrilic chloride tripolymer crystalline solid；
2. hydroxyl phosphonitrilic chloride tripolymer and hydroquinones, tetrachloroethanes are hydroxyl phosphonitrilic chloride tripolymer by weight: right
Benzenediol: tetrachloroethanes=100: 50~200: 400~600 ratio input reactor, nitrogen protection is passed through, stirring is started, rise
To 130~220 DEG C, polycondensation reaction 5~10 hours, vacuum distillation removes tetrachloroethanes, cooling, with petroleum ether dissolution, plus steaming to temperature
Distilled water, stirring is stood, and takes oil phase, vacuum distillation removing petroleum ether, then is dissolved with tetrahydrofuran, filtered, and vacuum drying is obtained
Hydroxyl phosphonitrilic resin.
The advantage of the invention is that：1st, hydroxylamine hydrochloride and phosphorus trichloride, chlorine reaction directly generate hydroxyl phosphonitrilic chloride
Tripolymer, can just introduce oh group since reaction, and such preparation method is few with respect to step, and it is convenient to react.2nd, with three
Phosphorus chloride chlorination gas can improve the yield of hydroxyl phosphonitrilic chloride tripolymer as raw material.3rd, made with pyridine and waterless cobaltous chloride
It is synergistic catalyst, can largely shortens the reaction time, improves product yield.4th, the hydroxyl phosphonitrilic resin of generation can be with
Rise with temperature and voluntarily solidify, largely reduce the solidification difficulty and solidification cost of conventional phosphonitrilic resin, the resin is existed
The application in the fields such as coating is provided a great convenience.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
Embodiment 1：
1. in hydroxylamine hydrochloride 100, phosphorus trichloride 200, tetrachloroethanes 500, pyridine 4 and waterless cobaltous chloride 2 being put into reactor, lead to
Enter chlorine 60, start stirring, be heated to 70 DEG C, flow back 5 hours, 60 DEG C are cooled to after the completion of reaction, filtering is removed unreacted
Cobalt chloride, then vacuum distillation removes unreacted phosphorus trichloride, pyridine and tetrachloroethanes respectively again, adds petroleum ether dissolution to obtain
After the solid for arriving, washed with the dilute sulfuric acid of percentage by weight 5%, point liquid stays oil phase, vacuum distillation removing petroleum ether to obtain yellowish
Color hydroxyl phosphonitrilic chloride tripolymer crystalline solid.
2. hydroxyl phosphonitrilic chloride tripolymer 100, hydroquinones 50, tetrachloroethanes 400 are put into reactor, is passed through nitrogen
Gas, starts stirring, is warming up to 130 DEG C, polycondensation reaction 5 hours, and vacuum distillation removes tetrachloroethanes, cooling, with petroleum ether dissolution,
Plus distilled water, stirring, stand, oil phase, vacuum distillation removing petroleum ether are taken, then dissolved with tetrahydrofuran, filtered, vacuum drying,
Obtain hydroxyl phosphonitrilic resin.
Embodiment 2：
1. in hydroxylamine hydrochloride 100, phosphorus trichloride 400, tetrachloroethanes 800, pyridine 50 and waterless cobaltous chloride 20 being put into reactor,
Chlorine 240 is passed through, stirring is started, 150 DEG C are heated to, flowed back 15 hours, 80 DEG C are cooled to after the completion of reaction, filtering is removed not
The cobalt chloride of reaction, then vacuum distillation removes unreacted phosphorus trichloride, pyridine and tetrachloroethanes respectively again, adds petroleum ether
After the solid that dissolving is obtained, washed with the dilute sulfuric acid of percentage by weight 10%, point liquid stays oil phase, vacuum distillation removing petroleum ether to obtain
To faint yellow hydroxyl phosphonitrilic chloride tripolymer crystalline solid.
2. hydroxyl phosphonitrilic chloride tripolymer 100, hydroquinones 200, tetrachloroethanes 600 are put into reactor, is passed through nitrogen
Gas, starts stirring, is warming up to 220 DEG C, and polycondensation reaction 10 hours, vacuum distillation removes tetrachloroethanes, and cooling is molten with petroleum ether
Solve, plus distilled water, stirring, stand, oil phase, vacuum distillation removing petroleum ether are taken, then dissolved with tetrahydrofuran, filtered, vacuum is done
It is dry, obtain hydroxyl phosphonitrilic resin.
Embodiment 3：
1. in hydroxylamine hydrochloride 100, phosphorus trichloride 300, tetrachloroethanes 600, pyridine 25 and waterless cobaltous chloride 10 being put into reactor,
Chlorine 150 is passed through, stirring is started, 120 DEG C are heated to, flowed back 10 hours, 70 DEG C are cooled to after the completion of reaction, filtering is removed not
The cobalt chloride of reaction, then vacuum distillation removes unreacted phosphorus trichloride, pyridine and tetrachloroethanes respectively again, adds petroleum ether
After the solid that dissolving is obtained, washed with the dilute sulfuric acid of percentage by weight 7%, point liquid stays oil phase, vacuum distillation removing petroleum ether to obtain
To faint yellow hydroxyl phosphonitrilic chloride tripolymer crystalline solid.
2. hydroxyl phosphonitrilic chloride tripolymer 100, hydroquinones 100, tetrachloroethanes 500 are put into reactor, is passed through nitrogen
Gas, starts stirring, is warming up to 170 DEG C, polycondensation reaction 8 hours, and vacuum distillation removes tetrachloroethanes, cooling, with petroleum ether dissolution,
Plus distilled water, stirring, stand, oil phase, vacuum distillation removing petroleum ether are taken, then dissolved with tetrahydrofuran, filtered, vacuum drying,
Obtain hydroxyl phosphonitrilic resin.
Embodiment 4：
1. in hydroxylamine hydrochloride 100, phosphorus trichloride 250, tetrachloroethanes 550, pyridine 15 and waterless cobaltous chloride 8 being put into reactor,
Chlorine 130 is passed through, stirring is started, 140 DEG C are heated to, flowed back 6 hours, 65 DEG C are cooled to after the completion of reaction, filtering is removed not anti-
The cobalt chloride answered, then vacuum distillation removes unreacted phosphorus trichloride, pyridine and tetrachloroethanes respectively again, adds petroleum ether molten
After the solid that solution is obtained, washed with the dilute sulfuric acid of percentage by weight 6%, point liquid stays oil phase, vacuum distillation removing petroleum ether to obtain
Faint yellow hydroxyl phosphonitrilic chloride tripolymer crystalline solid.
2. hydroxyl phosphonitrilic chloride tripolymer 100, hydroquinones 150, tetrachloroethanes 550 are put into reactor, is passed through nitrogen
Gas, starts stirring, is warming up to 150 DEG C, polycondensation reaction 7 hours, and vacuum distillation removes tetrachloroethanes, cooling, with petroleum ether dissolution,
Plus distilled water, stirring, stand, oil phase, vacuum distillation removing petroleum ether are taken, then dissolved with tetrahydrofuran, filtered, vacuum drying,
Obtain hydroxyl phosphonitrilic resin.
Claims (1)
1. a kind of preparation method of hydroxyl phosphonitrilic resin, its step：1. by raw material hydroxylamine hydrochloride, phosphorus trichloride, tetrachloroethanes,
Pyridine and waterless cobaltous chloride are with weight ratio as hydroxylamine hydrochloride: phosphorus trichloride: tetrachloroethanes: pyridine: cobalt chloride=100: 200~400
: in 500~800: 4~50: 2~20 ratio input reactor, it is passed through addition is phosphorus trichloride weight 30~60% chlorine
Gas, starts stirring, is heated to 70~150 DEG C, flows back 5~15 hours, and 60~80 DEG C are cooled to after the completion of reaction, and filtering is removed
Unreacted cobalt chloride, then vacuum distillation removes unreacted phosphorus trichloride, pyridine and tetrachloroethanes respectively again, adds oil
After the ether solid that obtains of dissolving, 5~10% dilute sulfuric acid of being weight percentage with concentration wash, stirred, standing, taking oil phase, decompression
Distillation removing petroleum ether, obtains faint yellow hydroxyl phosphonitrilic chloride tripolymer crystalline solid；2. by hydroxyl phosphonitrilic chloride tripolymer
By weight it is hydroxyl phosphonitrilic chloride tripolymer: hydroquinones: tetrachloroethanes=100 with hydroquinones, tetrachloroethanes: 50~
200: 400~600 ratio input reactor, is passed through nitrogen protection, starts stirring, is warming up to 130~220 DEG C, polycondensation reaction 5
~10 hours, vacuum distillation removed tetrachloroethanes, and cooling with petroleum ether dissolution, plus distilled water, is stirred, stood, and takes oil phase, is subtracted
Pressure distillation removing petroleum ether, then dissolved with tetrahydrofuran, filtered, vacuum drying obtains hydroxyl phosphonitrilic resin.
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| CN201710081344.3A CN106832302A (en) | 2017-02-15 | 2017-02-15 | A kind of preparation method of hydroxyl phosphonitrilic resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651989A (en) * | 2018-12-07 | 2019-04-19 | 江西省科学院应用化学研究所 | A kind of preparation method of high temperature resistant toughness adhesive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1241346A (en) * | 1968-06-26 | 1971-08-04 | Nord Aviation | Polymeric products derived from phosphonitrile chloride |
-
2017
- 2017-02-15 CN CN201710081344.3A patent/CN106832302A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1241346A (en) * | 1968-06-26 | 1971-08-04 | Nord Aviation | Polymeric products derived from phosphonitrile chloride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651989A (en) * | 2018-12-07 | 2019-04-19 | 江西省科学院应用化学研究所 | A kind of preparation method of high temperature resistant toughness adhesive |
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Application publication date: 20170613 |