CN104974351B - A kind of carboxy blocking phosphorous-containing polyester and its preparation method and application - Google Patents
A kind of carboxy blocking phosphorous-containing polyester and its preparation method and application Download PDFInfo
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- CN104974351B CN104974351B CN201510483164.9A CN201510483164A CN104974351B CN 104974351 B CN104974351 B CN 104974351B CN 201510483164 A CN201510483164 A CN 201510483164A CN 104974351 B CN104974351 B CN 104974351B
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Abstract
The invention discloses phosphorous-containing polyesters of a kind of carboxy blocking and its preparation method and application to have synthesized the phosphorus-containing polyester fire retardant type curing agent of carboxy blocking using the phosphorous-containing polyester of phenolic hydroxyl group sealing end, alkylene oxides monomer, anhydride as reaction raw materials.Flame retardant type curing agent is introduced into epoxy-resin systems by preparing flame retardant type curing agent, and in Curing Process of Epoxy, has prepared the epoxy resin of high flame retardant, and does not influence other performances of epoxy resin.
Description
Technical field
The invention belongs to thermosetting resin preparation technical field, it is related to a kind of carboxy blocking phosphorous-containing polyester and preparation method thereof
And application.
Background technique
High molecular material has been widely used for the fields such as building, electronic device, traffic, but has to the anti-flammability of material
The occasion of high requirement cannot be applied directly, it is therefore necessary to the anti-flammability of reinforcing material.Height is reduced using fire retardant
The anti-flammability of molecular material is to prepare one of main path of flame retarded polymeric material.According to the difference of ignition-proof element, fire retardant
The flame-retardant systems such as halogen, nitrogen, boron, antimony, magnesium, phosphorus can be divided into, wherein halogen containing flame-retardant can generate a large amount of corrosivity in burning
Object and a large amount of toxic gas, life and environment to the mankind generate secondary injury, thus its development is limited by very large.
Sight is gradually transferred on halogen-free flame retardants by people, and phosphonium flame retardant is a kind of nothing important, with wide application prospect
Halogen fire retardant.Contain a small amount of phosphonium flame retardant in high molecular material, can significantly improve the anti-flammability of polymer material.Contain
Phosphorus fire retardant can be divided into addition type and response type two major classes.The phosphonium flame retardant of addition type is in processing of high molecular material process
Middle addition phosphorus or compound and it is present in basis material in a manner of physical dispersion, to improve the anti-flammability of material.But
Be addition type phosphonium flame retardant usually require addition amount it is big, the amount for generally requiring addition 20~40% (mass fraction) could reach
To good flame retardant effect, and the phosphonium flame retardant of addition type usually with the poor compatibility of basis material, in use
It is easy that the mechanical property for reducing material is precipitated.Response type phosphonium flame retardant is to introduce to join during synthesis of polymer material
It with the phosphorus containing components reacted, is not migrated to reach ignition-proof element, flame retardant property is permanent, and dimensional stability is high, oxidation stability
By force, in multi-purpose and thermoset macromolecule material.Epoxy resin navigates as a kind of universal thermoset macromolecule material in aviation
It, Electronic Packaging, the fields such as communications and transportation be all widely used, but general purpose epoxy resin material easy firing, limit oxygen refer to
Number only 19.8, therefore, in many application fields it is necessary to its flame retardant property of raising.And it is based on fire-retardant non-halogen development trend
Influence with additive flame retardant to material performance itself researches and develops response type halogen-free flame retardants to improve the anti-flammability of epoxy resin
Have become the research hotspot of scholars.
Summary of the invention
In view of the foregoing, it is an object to a kind of novel carboxylic sealing end phosphorous-containing polyester is provided, it is fire-retardant by preparing
Type curing agent, is introduced into epoxy-resin systems in Curing Process of Epoxy, can significantly improve epoxy resin
Anti-flammability.Specific technical solution is as follows:
A kind of phosphorous-containing polyester of carboxy blocking, has the following structure formula:
Wherein, n is natural number；
R1And R2Selected from following group:
R3Selected from methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl,
R4It is selected from
R5It is selected from
The preparation method of the phosphorous-containing polyester of above-mentioned carboxy blocking, which comprises the steps of:
(1) phosphorous-containing polyester is dissolved in solvent and is made into the solution of 40~50wt% as initiator, initiator, antioxidant,
Catalyst is added in polymerization reaction kettle, and ventilation vacuumizes three times repeatedly, under nitrogen protection, monomer, control reaction is continuously added dropwise
Reaction is until pressure no longer declines temperature after 100~110 DEG C and reaction pressure are in 0.4~0.8MPa, charging, water flowing
Decrease temperature and pressure, being cooled to room temperature normal pressure, reaction was completed；Then, phosphoric acid is added and stirs 0.5~1h, adsorbent is added to resulting
In compound, stirring at normal temperature reacts 0.5h~1h, the phosphorous-containing polyester of alcoholic extract hydroxyl group sealing end is obtained after filtering；
The additional amount of the phosphoric acid is that n (phosphoric acid)/n (catalyst) is 0.3~0.8；
The weight percent that the dosage of antioxidant accounts for initiator is 0.1~0.3%；
The weight percent that the dosage of catalyst accounts for initiator is 0.1~1%；
The weight percent that the dosage of monomer accounts for initiator is 20~30%；
The weight percent that the dosage of adsorbent accounts for mixture is 1~8%；
(2) phosphorous-containing polyester of the sealing end of alcoholic extract hydroxyl group obtained in step 1, acid anhydrides are dissolved in organic solvent, wherein phosphorous poly-
The molar ratio of ester and acid anhydrides is 1:2.5~1:3, is made into the solution of 40wt%, and imidazoles is added or pyridines catalyst, content are anti-
0.1~0.3wt% of object is answered, under argon gas protection, control reaction temperature reacts 6h under 50~70 DEG C, mechanical agitation, instead
Dissolution precipitating obtains the phosphorous-containing polyester of carboxy blocking afterwards three times repeatedly in appropriate solvent after answering.
Phosphorous-containing polyester described in step (1) has the following structure formula:
The structural formula of the phosphorous-containing polyester of step (1) the alcoholic extract hydroxyl group sealing end is as follows:
。
Step (1) solvent is the mixing of one or more of dimethylformamide, tetrahydrofuran, dioxane
Object；
The antioxidant is butylhydroxy fennel, dibutyl hydroxy toluene, propylgallate, 2,6- di-t-butyl to first
Phenol, bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers or four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) Ji Wusi
The mixture of alcohol ester one or more；
The catalyst is alkali metal, alkaline earth oxide, hydroxide, alkoxide or its anion active kind；
The adsorbent is diatomite.
Step (1) described monomer is the mixture of one or more of ethylene oxide, propylene oxide, epoxy butane.
Step (2) described acid anhydrides is maleic anhydride, succinic anhydride or phthalic anhydride；
The imidazoles or pyridines catalyst are imidazoles, 1- methylimidazole, 2-methylimidazole or 4-dimethylaminopyridine；
The organic solvent is N,N-dimethylformamide, dioxane or tetrahydrofuran.
The curing agent of the application of the phosphorous-containing polyester of above-mentioned carboxy blocking and methyl tetrahydro phthalic anhydride together as epoxy resin
It is applied in epoxy resin, obtains fire-retardant epoxy resin.
The phosphorous-containing polyester of the carboxy blocking and the mass percent of methyl tetrahydro phthalic anhydride are 25-100wt%.
When the weight that the phosphorous-containing polyester of the carboxy blocking accounts for the epoxy resin is 30%, the pole of the epoxy resin
What limited oxygen index never added phosphorous-containing polyester 19.8% is raised to 32.9%.
Advantages of the present invention: having synthesized a kind of fire retardant of response type, will not migrate during use, usage amount compared with
The anti-flammability of epoxy resin can be effectively improved in the case where few, and the mechanical performance of epoxy resin itself is not broken
It is bad, there is biggish promotion instead.
Detailed description of the invention
Fig. 1 is the infrared spectrum of phosphorus-containing polyester fire retardant curing agent synthesized by embodiment 1；
Fig. 2 is the nucleus magnetic hydrogen spectrum of phosphorus-containing polyester fire retardant curing agent synthesized by embodiment 1；
Fig. 3 is the nuclear-magnetism phosphorus spectrum of phosphorus-containing polyester fire retardant curing agent synthesized by embodiment 1.
Specific embodiment
In the following, specific embodiments of the present invention are further described in detail in conjunction with the accompanying drawings and embodiments, but do not answer
It is limited the scope of the invention with this.
Embodiment 1
(1) by 0.5mol phosphorous-containing polyester be dissolved in tetrahydrofuran after be added polymerization reaction kettle in, be added 0.1wt%KOH and
0.1wt% tetra- (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythritol ester, vacuumizes, and three times, argon gas is protected for ventilation
Shield, vacuumizes 0.5h, minor amount of water in removing system；
(2) 4mol propylene oxide is continuously added dropwise in the product obtained to step (1) to be reacted, reaction temperature be 120~
130 DEG C, control pressure is 0.4~0.6MPa, after charging, indicates that reaction terminates when reaction pressure is down to constant, leads to argon
Gas replaces in kettle residual gas to normal pressure；
(3) by n (H in the product obtained to step (2)3PO4)/n(K+) it is that 0.6:1 adds phosphoric acid and 5wt% kieselguhr adsorption
Agent obtains the phosphorous-containing polyester of alcoholic extract hydroxyl group sealing end after filtering；
(4) product, succinic anhydride obtained in step 3 are dissolved in dioxane, wherein control alcoholic extract hydroxyl group sealing end contains
The molar ratio of phosphorus polyester and succinic anhydride is 1:2, and controlling total solid content is 40%, 1- methylimidazole is added as catalyst,
Under protection of argon gas, after mechanic whirl-nett reaction 6h, product is precipitated in ether, the volume ratio for controlling solvent and precipitating reagent is 1:
10, three times, place the product in dry to obtain containing for the carboxy blocking to constant weight in 70 DEG C of vacuum drying ovens for dissolution precipitating repeatedly
Phosphorus polyester, infrared spectrum, nucleus magnetic hydrogen spectrum, nuclear-magnetism phosphorus spectrum are as shown in Figure 1, Figure 2, Figure 3 shows respectively.
Embodiment 2
(1) by 0.5mol phosphorous-containing polyester be dissolved in tetrahydrofuran after be added polymerization reaction kettle in, be added 0.1wt%KOH and
0.1wt% tetra- (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythritol ester, vacuumizes, and three times, argon gas is protected for ventilation
Shield controls 90 DEG C of temperature, vacuumizes 0.5h, minor amount of water in removing system；
(2) 4mol propylene oxide is continuously added dropwise in the product obtained to step (1) to be reacted, reaction temperature be 120~
130 DEG C, control pressure is 0.4~0.6MPa, after charging, indicates that reaction terminates when reaction pressure is down to constant, leads to argon
Gas replaces in kettle residual gas to normal pressure；
(3) by n (H in the product obtained to step (2)3PO4)/n(K+) it is that 0.6:1 adds phosphoric acid and 5wt% kieselguhr adsorption
Agent obtains the phosphorous-containing polyester of alcoholic extract hydroxyl group sealing end after filtering；
(4) product obtained in step 3 and maleic anhydride are dissolved in tetrahydrofuran, control hydroxy-end capped phosphorous-containing polyester
Molar ratio with maleic anhydride is 1:2, and controlling total solid content is 40%, and addition pyridine is as catalyst, under protection of argon gas,
Reaction temperature is controlled at 50 DEG C, mixture precipitates in ether after reacting 6h under mechanical stirring, controls the body of solvent and precipitating reagent
Product is than being 1:10, and dissolution dissolution precipitating three times, place the product in drying in 70 DEG C of vacuum drying ovens to constant weight, obtains described repeatedly
The phosphorous-containing polyester of carboxy blocking, infrared spectrum, nucleus magnetic hydrogen spectrum, nuclear-magnetism phosphorus spectrum are similar with Fig. 1, Fig. 2, Fig. 3 respectively.
Embodiment 3
(1) by 0.5mol phosphorous-containing polyester be dissolved in tetrahydrofuran after be added polymerization reaction kettle in, be added 0.1wt%KOH and
0.1wt%2,6- di-tert-butyl p-cresol, vacuumize, and three times, argon gas protection controls 90 DEG C of temperature, vacuumizes 0.5h, remove for ventilation
Go minor amount of water in system；
(2) 4mol ethylene oxide is continuously added dropwise in the product obtained to step (1) to be reacted, reaction temperature be 120~
130 DEG C, control pressure is 0.4~0.6MPa, after charging, indicates that reaction terminates when reaction pressure is down to constant, leads to argon
Gas replaces in kettle residual gas to normal pressure；
(3) by n (H in the product obtained to step (2)3PO4)/n(K+) it is that 0.6:1 adds phosphoric acid and 5wt% kieselguhr adsorption
Agent obtains the phosphorous-containing polyester of alcoholic extract hydroxyl group sealing end after filtering；
(4) product, maleic anhydride obtained in step 3 are dissolved in tetrahydrofuran, wherein control alcoholic extract hydroxyl group sealing end contains
The molar ratio of phosphorus polyester and maleic anhydride is 1:2, and controlling total solid content is 40%, 1- methylimidazole is added as catalyst,
Under protection of argon gas, after mechanic whirl-nett reaction 6h, product is precipitated in ether, the volume ratio for controlling solvent and precipitating reagent is 1:
10, three times, place the product in dry to obtain containing for the carboxy blocking to constant weight in 70 DEG C of vacuum drying ovens for dissolution precipitating repeatedly
Phosphorus polyester, infrared spectrum, nucleus magnetic hydrogen spectrum, nuclear-magnetism phosphorus spectrum are similar with Fig. 1, Fig. 2, Fig. 3 respectively.
Embodiment 4
(1) by 0.5mol phosphorous-containing polyester be dissolved in tetrahydrofuran after be added polymerization reaction kettle in, be added 0.1wt%KOH and
0.1wt%2,6- di-tert-butyl p-cresol, vacuumize, and three times, argon gas protection controls 90 DEG C of temperature, vacuumizes 0.5h, remove for ventilation
Go minor amount of water in system；
(2) 4mol epoxy butane is continuously added dropwise in the product obtained to step (1) to be reacted, reaction temperature be 120~
130 DEG C, control pressure is 0.4~0.6MPa, after charging, indicates that reaction terminates when reaction pressure is down to constant, leads to argon
Gas replaces in kettle residual gas to normal pressure；
(3) by n (H in the product obtained to step (2)3PO4)/n(K+) it is that 0.7:1 adds phosphoric acid and 5wt% adsorption of magnesium silicate
Agent obtains the phosphorous-containing polyester of alcoholic extract hydroxyl group sealing end after filtering；
(4) product, phthalic anhydride obtained in step 3 are dissolved in tetrahydrofuran, wherein control alcoholic extract hydroxyl group sealing end
Phosphorous-containing polyester and phthalic anhydride molar ratio be 1:2, control total solid content be 40%, be added 4-dimethylaminopyridine
As catalyst, under protection of argon gas, after mechanic whirl-nett reaction 6h, product is precipitated in ether, controls solvent and precipitating reagent
Volume ratio be 1:10, dissolution precipitating three times, place the product in drying in 70 DEG C of vacuum drying ovens to constant weight, obtains described repeatedly
The phosphorous-containing polyester of carboxy blocking, infrared spectrum, nucleus magnetic hydrogen spectrum, nuclear-magnetism phosphorus spectrum are similar with Fig. 1, Fig. 2, Fig. 3 respectively.
Embodiment 5
The present embodiment be the carboxy blocking for obtaining embodiment 1 to 4 phosphorous-containing polyester as curing agent in the epoxy
Concrete application, and methyl tetrahydro phthalic anhydride is applied in epoxy resin together as the curing agent of epoxy resin, obtains fire-retardant
Type epoxy resin；The phosphorous-containing polyester of the carboxy blocking and the mass percent of methyl tetrahydro phthalic anhydride are 25-100%.
When the mass percent that the dosage of the phosphorous-containing polyester of carboxy blocking accounts for whole system reaches 30wt%, epoxy resin
Limit oxygen index never add the 19.8% of phosphorous-containing polyester and be raised to 32.9%.
Claims (7)
1. a kind of phosphorous-containing polyester of carboxy blocking, which is characterized in that the phosphorous-containing polyester of the carboxy blocking has the following structure formula:
Wherein, n is natural number；
R1And R2Selected from following group:
R3Selected from methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl,
R4Selected from-CH2-CH2-、
R5It is selected from
2. the preparation method of the phosphorous-containing polyester of carboxy blocking described in claim 1, which comprises the steps of:
(1) phosphorous-containing polyester is dissolved in solvent and is made into the solution of 40~50wt% as initiator, initiator, antioxidant, catalysis
Agent is added in polymerization reaction kettle, and ventilation vacuumizes three times repeatedly, under nitrogen protection, monomer is continuously added dropwise, controls reaction temperature
Reaction is until pressure no longer declines after 100~110 DEG C and reaction pressure are in 0.4~0.8MPa, charging, water flowing cooling
Decompression, being cooled to room temperature normal pressure, reaction was completed；Then, after phosphoric acid stirring 0.5~1h catalyst neutralisation is added, adsorbent is added
Into resulting compound, stirring at normal temperature reacts 0.5~1h, removes unreacted catalyst and antioxidant, obtains alcohol after filtering
Hydroxy-end capped phosphorous-containing polyester；
The additional amount of the phosphoric acid is that phosphoric acid/catalyst molar ratio is 0.3~0.8；
The weight percent that the dosage of antioxidant accounts for initiator is 0.1~0.3%；
The weight percent that the dosage of catalyst accounts for initiator is 0.1~1%；
The weight percent that the dosage of monomer accounts for initiator is 20~30%；
The weight percent that the dosage of adsorbent accounts for mixture is 1~8%；
(2) it is 1 by the molar ratio of phosphorous-containing polyester and acid anhydrides by the phosphorous-containing polyester of the sealing end of alcoholic extract hydroxyl group obtained in step 1 and acid anhydrides:
2.5~1:3 is dissolved in organic solvent, is made into the solution of 40wt%, and the imidazoles or pyridines catalyst of 0.1~0.3wt%, argon is added
Under gas shielded, in 50~70 DEG C of reaction 6h under mechanical agitation, after reaction, dissolution precipitates three repeatedly in appropriate solvent
The phosphorous-containing polyester of carboxy blocking is obtained after secondary；
Phosphorous-containing polyester described in the step (1) has the following structure formula:
Wherein, n is natural number；
R1And R2Selected from following group:
R3Selected from methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl,
The step (1) monomer is ethylene oxide, propylene oxide or epoxy butane；
The step (1) catalyst is potassium hydroxide；
The structural formula of the phosphorous-containing polyester of step (1) the alcoholic extract hydroxyl group sealing end is as follows:
Wherein R1And R2Selected from following group:
R3Selected from methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl,
R4Selected from-CH2-CH2-、
3. preparation method according to claim 2, which is characterized in that step (1) solvent is dimethylformamide, four
The mixture of one or more of hydrogen furans, dioxane；
The antioxidant be butylhydroxy fennel, dibutyl hydroxy toluene, propylgallate, DBPC 2,6 ditertiary butyl p cresol,
Bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers or four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythrites
Ester；
The adsorbent is diatomite.
4. preparation method according to claim 2, which is characterized in that step (2) described acid anhydrides is maleic anhydride, succinic acid
Acid anhydride or phthalic anhydride；
The imidazoles or pyridines catalyst are imidazoles, 1- methylimidazole, 2-methylimidazole or 4-dimethylaminopyridine；
The organic solvent is N,N-dimethylformamide, dioxane or tetrahydrofuran.
5. the application of the phosphorous-containing polyester of carboxy blocking described in claim 1, which is characterized in that the phosphorous of the carboxy blocking gathers
Ester and methyl tetrahydro phthalic anhydride are applied in epoxy resin together as the curing agent of epoxy resin, obtain fire-retardant epoxy resin.
6. application according to claim 5, which is characterized in that the phosphorous-containing polyester of the carboxy blocking accounts for methyl tetrahydro phthalic anhydride
Mass percent be 25~50%.
7. application according to claim 5, which is characterized in that when the phosphorous-containing polyester of the carboxy blocking accounts for the asphalt mixtures modified by epoxy resin
When the weight of rouge is 30%, the limit oxygen index of the epoxy resin is raised to 32.9% from 19.8%.
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| CN111087612B (en) * | 2018-10-23 | 2022-07-12 | 今创景新材料科技（上海）有限公司 | Phosphorus-containing flame-retardant nylon and preparation method and application thereof |
| CN111087796B (en) * | 2018-10-23 | 2022-07-12 | 今创景新材料科技（上海）有限公司 | Phosphorus-containing copolymerized nylon and preparation method and application thereof |
| CN112358709A (en) * | 2020-10-30 | 2021-02-12 | 今创景新材料科技（上海）有限公司 | Preparation method of degradable polyester foam material |
| CN112321996A (en) * | 2020-10-30 | 2021-02-05 | 今创景新材料科技（上海）有限公司 | Phosphorus-containing flame-retardant degradable polyester material and preparation method thereof |
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| TWI471350B (en) * | 2010-05-12 | 2015-02-01 | Taiwan Union Technology Corp | Halogen-free flame-retardant epoxy resin composition, and prepreg and printed wiring board using the same |
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