CN104974351A - Carboxy-terminated phosphorus-containing polyester as well as preparation method and application thereof - Google Patents
Carboxy-terminated phosphorus-containing polyester as well as preparation method and application thereof Download PDFInfo
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- CN104974351A CN104974351A CN201510483164.9A CN201510483164A CN104974351A CN 104974351 A CN104974351 A CN 104974351A CN 201510483164 A CN201510483164 A CN 201510483164A CN 104974351 A CN104974351 A CN 104974351A
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Abstract
The invention discloses a carboxy-terminated phosphorus-containing polyester as well as a preparation method and an application thereof. A carboxy-terminated phosphorus-containing polyester inflaming-retarding curing agent is synthesized of phenolic hydroxy-terminated phosphorus-containing polyester, alkylene oxide monomer and anhydrides. By preparing an inflaming-retarding curing agent and introducing the inflaming-retarding curing agent into an epoxy resin system in the epoxy resin curing process, the high inflaming-retarding epoxy resin can be prepared, and other properties of the epoxy resin cannot be affected.
Description
Technical field
The invention belongs to thermosetting resin preparing technical field, relate to a kind of carboxy blocking phosphorous-containing polyester and its preparation method and application.
Background technology
Macromolecular material has been widely used in the fields such as building, electron device, traffic, but to the occasion that the flame retardant resistance of material has higher requirements, can not directly be applied, and is therefore necessary the flame retardant resistance of strongthener.The flame retardant resistance adopting fire retardant to reduce macromolecular material is one of main path preparing flame retarded polymeric material.According to the difference of ignition-proof element, fire retardant can be divided into the flame-retardant systems such as halogen, nitrogen, boron, antimony, magnesium, phosphorus, wherein halogen containing flame-retardant can produce a large amount of corrosive goodses and a large amount of toxic gases when burning, to life and the environment generation secondary injury of the mankind, thus its development is limited by very large.Sight is transferred on halogen-free flame retardants by people gradually, and phosphonium flame retardant is the halogen-free flame retardants that a class is important, have wide application prospect.Containing a small amount of phosphonium flame retardant in macromolecular material, the flame retardant resistance of polymer materials just can be improved significantly.Phosphonium flame retardant can be divided into addition type and the large class of response type two.The phosphonium flame retardant of addition type in processing of high molecular material process, adds phosphorus or compound and is present in body material in physical dispersion mode, thus improve the flame retardant resistance of material.But addition type phosphonium flame retardant needs the amount of interpolation large usually, generally need the amount of interpolation 20 ~ 40% (massfraction) just can reach good flame retardant effect, and the phosphonium flame retardant of addition type is usual and the poor compatibility of body material, in use easily separates out the mechanical property reducing material.Response type phosphonium flame retardant is in synthesis of polymer material process, introduce the phosphorus containing components that can participate in reacting, thus reaches ignition-proof element and do not move, and flame retardant properties is permanent, and dimensional stability is high, and oxidative stability is strong, multiplex with thermoset macromolecule material.Epoxy resin is as a kind of universal thermoset macromolecule material, all be widely used in fields such as aerospace, Electronic Packaging, communications and transportation, but general purpose epoxy resin material easy firing, limiting oxygen index(LOI) only has 19.8, therefore, be all necessary to improve its flame retardant properties in many Application Areass.And based on fire-retardant non-halogen development trend and additive flame retardant on the impact of the performance of material own, the flame retardant resistance that research and development response type halogen-free flame retardants improves epoxy resin has become the study hotspot of scholars.
Summary of the invention
In view of above problem, the object of this invention is to provide a kind of novel carboxylic end-blocking phosphorous-containing polyester, by preparing flame retardant type solidifying agent, being introduced in epoxy-resin systems in Curing Process of Epoxy, the flame retardant resistance of epoxy resin can be significantly improved.Concrete technical scheme is as follows:
A phosphorous-containing polyester for carboxy blocking, has following structural formula:
Wherein, n is natural number;
R
1and R
2be selected from following group:
R
3be selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl,
R
4be selected from
R
5be selected from
The preparation method of the phosphorous-containing polyester of above-mentioned carboxy blocking, is characterized in that, comprises the steps:
(1) phosphorous-containing polyester is dissolved in solvent and is made into the solution of 40 ~ 50wt% as initiator, initiator, oxidation inhibitor, catalyzer are added in polymerization reaction kettle, ventilation vacuumizes three times repeatedly, under nitrogen protection, continuous dropping monomer, controls temperature of reaction 100 ~ 110 DEG C and reaction pressure at 0.4 ~ 0.8MPa, reacts to pressure no longer declines after reinforced, water flowing decrease temperature and pressure, is cooled to normal temperature and pressure and terminates reaction; Then, add phosphoric acid and stir 0.5 ~ 1h catalyst neutralisation, joined by sorbent material in the compound of gained, stirring at normal temperature reaction 0.5h ~ 1h, removes unreacted catalyzer and oxidation inhibitor, obtains the phosphorous-containing polyester of alcoholic extract hydroxyl group end-blocking after filtration;
The add-on of described phosphoric acid is n (acid)/n (metal ion) is 0.3 ~ 0.8;
The weight percent that the consumption of oxidation inhibitor accounts for initiator is 0.1 ~ 0.3%;
The weight percent that the consumption of catalyzer accounts for initiator is 0.1 ~ 1%;
The weight percent that the consumption of monomer accounts for initiator is 20 ~ 30%;
The weight percent that the consumption of sorbent material accounts for mixture is 1 ~ 8%;
(2) phosphorous-containing polyester of the alcoholic extract hydroxyl group end-blocking obtained in step 1, acid anhydrides are dissolved in organic solvent; wherein the mol ratio of phosphorous-containing polyester and acid anhydrides is 1:2.5 ~ 1:3; be made into the solution of 40wt%; add imidazoles or pyridines catalyzer; content is 0.1 ~ 0.3wt% of reactant, under argon shield, controls temperature of reaction at 50 ~ 70 DEG C; react 6h under mechanical agitation, in appropriate solvent, after reaction terminates, repeatedly obtain the phosphorous-containing polyester of carboxy blocking after dissolution precipitation three times.
Described in step (1), phosphorous-containing polyester has following structural formula:
The structural formula of the phosphorous-containing polyester of step (1) described alcoholic extract hydroxyl group end-blocking is as follows:
Step (1) described solvent is the mixture of one or more in dimethyl formamide, tetrahydrofuran (THF), dioxane;
Described oxidation inhibitor is butylhydroxy fennel, butylated hydroxytoluene, Tenox PG, 2,6-ditertbutylparacresol, two (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether or four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester;
Described catalyzer is basic metal, alkaline earth metal oxide, oxyhydroxide, alkoxide or its anion active kind;
Described sorbent material is diatomite.
Step (1) described monomer is the mixture of one or more in oxyethane, propylene oxide, tetrahydrofuran (THF), butylene oxide ring.
Step (2) described acid anhydrides is maleic anhydride, Succinic anhydried or Tetra hydro Phthalic anhydride;
Described imidazoles or pyridines catalyzer are imidazoles, 1-Methylimidazole, glyoxal ethyline or DMAP;
Described organic solvent is DMF, dioxane or tetrahydrofuran (THF).
The application of the phosphorous-containing polyester of above-mentioned carboxy blocking, is applied in epoxy resin as the solidifying agent of epoxy resin, obtains fire-retardant epoxy resin together with methyl tetrahydro phthalic anhydride.
The phosphorous-containing polyester of described carboxy blocking and the mass percent of methyl tetrahydro phthalic anhydride are 25-100wt%.
When the weight that the phosphorous-containing polyester of described carboxy blocking accounts for described epoxy resin is 30%, the limiting oxygen index(LOI) of described epoxy resin never adds 19.8% of phosphorous-containing polyester and is raised to 32.9%.
Advantage of the present invention: synthesized a kind of fire retardant of response type, can not move in the process used, just effectively can improve the flame retardant resistance of epoxy resin when usage quantity is less, and the mechanical property of epoxy resin itself is not destroyed, have larger lifting on the contrary.
Accompanying drawing explanation
The infrared spectrum of the phosphorus-containing polyester fire retardant solidifying agent of Fig. 1 synthesized by embodiment 1;
The nucleus magnetic hydrogen spectrum of the phosphorus-containing polyester fire retardant solidifying agent of Fig. 2 synthesized by embodiment 1;
The nuclear-magnetism phosphorus spectrum of the phosphorus-containing polyester fire retardant solidifying agent of Fig. 3 synthesized by embodiment 1.
Embodiment
Below, specific embodiments of the present invention are further described in detail in conjunction with the accompanying drawings and embodiments, but should not limit the scope of the invention with this.
Embodiment 1
(1) 0.5mol phosphorous-containing polyester is dissolved in after in tetrahydrofuran (THF) adds in polymerization reaction kettle, add 0.1wt%KOH and 0.1wt% tetra-(β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester, vacuumize, take a breath three times, argon shield, vacuumizes 0.5h, minor amount of water in removing system;
(2) drip 4mol propylene oxide in the product obtained to step (1) continuously to react, temperature of reaction is 120 ~ 130 DEG C, control pressure is 0.4 ~ 0.6MPa, after reinforced end, question response Pressure Drop is to representing time constant that reaction terminates, logical argon gas, in displacement still, residual gas is to normal pressure;
(3) by n (H in the product obtained to step (2)
3pO
4)/n (K
+) for 0.6:1 adds phosphoric acid and 5wt% diatomite adsorbant, after filtration, namely obtain the phosphorous-containing polyester of alcoholic extract hydroxyl group end-blocking;
(4) product will obtained in step 3, Succinic anhydried is dissolved in dioxane, wherein the phosphorous-containing polyester of control alcoholic extract hydroxyl group end-blocking and the mol ratio of Succinic anhydried are 1:2, controlling total solid content is 40%, add 1-Methylimidazole as catalyzer, under argon shield, after mechanic whirl-nett reaction 6h, product is precipitated in ether, the volume ratio controlling solvent and precipitation agent is 1:10, dissolution precipitation three times repeatedly, product is placed in 70 DEG C of vacuum drying ovens and is dried to constant weight, obtain the phosphorous-containing polyester of described carboxy blocking, its infrared spectrum, nucleus magnetic hydrogen spectrum, nuclear-magnetism phosphorus spectrum is respectively as Fig. 1, Fig. 2, shown in Fig. 3.
Embodiment 2
(1) 0.5mol phosphorous-containing polyester is dissolved in after in tetrahydrofuran (THF) adds in polymerization reaction kettle, add 0.1wt%KOH and 0.1wt% tetra-(β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester, vacuumize, take a breath three times, argon shield, control temperature 90 DEG C, vacuumize 0.5h, minor amount of water in removing system;
(2) drip 4mol propylene oxide in the product obtained to step (1) continuously to react, temperature of reaction is 120 ~ 130 DEG C, control pressure is 0.4 ~ 0.6MPa, after reinforced end, question response Pressure Drop is to representing time constant that reaction terminates, logical argon gas, in displacement still, residual gas is to normal pressure;
(3) by n (H in the product obtained to step (2)
3pO
4)/n (K
+) for 0.6:1 adds phosphoric acid and 5wt% diatomite adsorbant, after filtration, namely obtain the phosphorous-containing polyester of alcoholic extract hydroxyl group end-blocking;
(4) product obtained in step 3 and maleic anhydride are dissolved in tetrahydrofuran (THF), the mol ratio controlling hydroxy-end capped phosphorous-containing polyester and maleic anhydride is 1:2, controlling total solid content is 40%, add pyridine as catalyzer, under argon shield, control temperature of reaction at 50 DEG C, after reacting 6h under mechanical stirring, mixture precipitates in ether, the volume ratio controlling solvent and precipitation agent is 1:10, repeatedly dissolve dissolution precipitation three times, product is placed in 70 DEG C of vacuum drying ovens and is dried to constant weight, obtain the phosphorous-containing polyester of described carboxy blocking, its infrared spectrum, nucleus magnetic hydrogen spectrum, nuclear-magnetism phosphorus spectrum respectively with Fig. 1, Fig. 2, Fig. 3 is similar.
Embodiment 3
(1) 0.5mol phosphorous-containing polyester is dissolved in after in tetrahydrofuran (THF) adds in polymerization reaction kettle, add 0.1wt%KOH and 0.1wt%2,6-ditertbutylparacresol, vacuumize, take a breath three times, argon shield, control temperature 90 DEG C, vacuumizes 0.5h, minor amount of water in removing system;
(2) drip 4mol oxyethane in the product obtained to step (1) continuously to react, temperature of reaction is 120 ~ 130 DEG C, control pressure is 0.4 ~ 0.6MPa, after reinforced end, question response Pressure Drop is to representing time constant that reaction terminates, logical argon gas, in displacement still, residual gas is to normal pressure;
(3) by n (H in the product obtained to step (2)
3pO
4)/n (K
+) for 0.6:1 adds phosphoric acid and 5wt% diatomite adsorbant, after filtration, namely obtain the phosphorous-containing polyester of alcoholic extract hydroxyl group end-blocking;
(4) product will obtained in step 3, maleic anhydride is dissolved in tetrahydrofuran (THF), wherein the phosphorous-containing polyester of control alcoholic extract hydroxyl group end-blocking and the mol ratio of maleic anhydride are 1:2, controlling total solid content is 40%, add 1-Methylimidazole as catalyzer, under argon shield, after mechanic whirl-nett reaction 6h, product is precipitated in ether, the volume ratio controlling solvent and precipitation agent is 1:10, dissolution precipitation three times repeatedly, product is placed in 70 DEG C of vacuum drying ovens and is dried to constant weight, obtain the phosphorous-containing polyester of described carboxy blocking, its infrared spectrum, nucleus magnetic hydrogen spectrum, nuclear-magnetism phosphorus spectrum respectively with Fig. 1, Fig. 2, Fig. 3 is similar.
Embodiment 4
(1) 0.5mol phosphorous-containing polyester is dissolved in after in tetrahydrofuran (THF) adds in polymerization reaction kettle, add 0.1wt%KOH and 0.1wt%2,6-ditertbutylparacresol, vacuumize, take a breath three times, argon shield, control temperature 90 DEG C, vacuumizes 0.5h, minor amount of water in removing system;
(2) drip 4mol butylene oxide ring in the product obtained to step (1) continuously to react, temperature of reaction is 120 ~ 130 DEG C, control pressure is 0.4 ~ 0.6MPa, after reinforced end, question response Pressure Drop is to representing time constant that reaction terminates, logical argon gas, in displacement still, residual gas is to normal pressure;
(3) by n (H in the product obtained to step (2)
3pO
4)/n (K
+) for 0.7:1 adds phosphoric acid and 5wt% magnesium silicate adsorbent, after filtration, namely obtain the phosphorous-containing polyester of alcoholic extract hydroxyl group end-blocking;
(4) product will obtained in step 3, Tetra hydro Phthalic anhydride is dissolved in tetrahydrofuran (THF), wherein the phosphorous-containing polyester of control alcoholic extract hydroxyl group end-blocking and the mol ratio of Tetra hydro Phthalic anhydride are 1:2, controlling total solid content is 40%, add DMAP as catalyzer, under argon shield, after mechanic whirl-nett reaction 6h, product is precipitated in ether, the volume ratio controlling solvent and precipitation agent is 1:10, dissolution precipitation three times repeatedly, product is placed in 70 DEG C of vacuum drying ovens and is dried to constant weight, obtain the phosphorous-containing polyester of described carboxy blocking, its infrared spectrum, nucleus magnetic hydrogen spectrum, nuclear-magnetism phosphorus spectrum respectively with Fig. 1, Fig. 2, Fig. 3 is similar.
Embodiment 5
The present embodiment be the phosphorous-containing polyester of the carboxy blocking that embodiment 1 to 4 is obtained as solidifying agent embody rule in the epoxy, it is applied in epoxy resin as the solidifying agent of epoxy resin together with methyl tetrahydro phthalic anhydride, obtains fire-retardant epoxy resin; The phosphorous-containing polyester of described carboxy blocking and the mass percent of methyl tetrahydro phthalic anhydride are 25 ~ 100%.
When the mass percent that the consumption of the phosphorous-containing polyester of carboxy blocking accounts for whole system reaches 30wt%, the limiting oxygen index(LOI) of epoxy resin never adds 19.8% of phosphorous-containing polyester and is raised to 32.9%.
Claims (10)
1. a phosphorous-containing polyester for carboxy blocking, is characterized in that, the phosphorous-containing polyester of described carboxy blocking has following structural formula:
Wherein, n is natural number;
R
1and R
2be selected from following group:
R
3be selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl,
R
4be selected from
R
5be selected from
2. the preparation method of the phosphorous-containing polyester of carboxy blocking according to claim 1, is characterized in that, comprises the steps:
(1) phosphorous-containing polyester is dissolved in solvent and is made into the solution of 40 ~ 50wt% as initiator, initiator, oxidation inhibitor, catalyzer are added in polymerization reaction kettle, ventilation vacuumizes three times repeatedly, under nitrogen protection, continuous dropping monomer, control temperature of reaction more than 100 ~ 110 DEG C and reaction pressure at 0.4 ~ 0.8MPa, feed in raw material after react to pressure no longer declines, water flowing decrease temperature and pressure, is cooled to normal temperature and pressure and terminates reaction; Then, after adding phosphoric acid stirring 0.5 ~ 1h catalyst neutralisation, joined by sorbent material in the compound of gained, stirring at normal temperature reaction 0.5 ~ 1h, removes unreacted catalyzer and oxidation inhibitor, obtains the phosphorous-containing polyester of alcoholic extract hydroxyl group end-blocking after filtration;
The add-on of described phosphoric acid is n (acid)/n (metal ion) is 0.3 ~ 0.8;
The weight percent that the consumption of oxidation inhibitor accounts for initiator is 0.1 ~ 0.3%;
The weight percent that the consumption of catalyzer accounts for initiator is 0.1 ~ 1%;
The weight percent that the consumption of monomer accounts for initiator is 20 ~ 30%;
The weight percent that the consumption of sorbent material accounts for mixture is 1 ~ 8%;
(2) be that 1:2.5 ~ 1:3 is dissolved in organic solvent by the phosphorous-containing polyester of the alcoholic extract hydroxyl group end-blocking obtained in step 1 and acid anhydrides by the mol ratio of phosphorous-containing polyester and acid anhydrides; be made into the solution of 40wt%; add imidazoles or the pyridines catalyzer of 0.1 ~ 0.3wt%; under argon shield; in 50 ~ 70 DEG C of reaction 6h under mechanical agitation; after reaction terminates, in appropriate solvent, repeatedly obtain the phosphorous-containing polyester of carboxy blocking after dissolution precipitation three times.
3. preparation method according to claim 2, is characterized in that, described in step (1), phosphorous-containing polyester has following structural formula:
4. preparation method according to claim 2, is characterized in that, the structural formula of the phosphorous-containing polyester of step (1) described alcoholic extract hydroxyl group end-blocking is as follows:
5. preparation method according to claim 2, is characterized in that, step (1) described solvent is the mixture of one or more in dimethyl formamide, tetrahydrofuran (THF), dioxane;
Described oxidation inhibitor is butylhydroxy fennel, butylated hydroxytoluene, Tenox PG, 2,6-ditertbutylparacresol, two (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether or four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester;
Described catalyzer is basic metal, alkaline earth metal oxide, oxyhydroxide, alkoxide or its anion active kind;
Described sorbent material is diatomite.
6. preparation method according to claim 2, is characterized in that, step (1) described monomer is the mixture of one or more in oxyethane, propylene oxide, tetrahydrofuran (THF), butylene oxide ring.
7. preparation method according to claim 2, is characterized in that, step (2) described acid anhydrides is maleic anhydride, Succinic anhydried or Tetra hydro Phthalic anhydride;
Described imidazoles or pyridines catalyzer are imidazoles, 1-Methylimidazole, glyoxal ethyline or DMAP;
Described organic solvent is DMF, dioxane or tetrahydrofuran (THF).
8. the application of the phosphorous-containing polyester of carboxy blocking according to claim 1, is characterized in that, the phosphorous-containing polyester of described carboxy blocking is applied in epoxy resin as the solidifying agent of epoxy resin together with methyl tetrahydro phthalic anhydride, obtains fire-retardant epoxy resin.
9. application according to claim 8, is characterized in that, the mass percent that the phosphorous-containing polyester of described carboxy blocking accounts for methyl tetrahydro phthalic anhydride is 25 ~ 50%.
10. application according to claim 8, is characterized in that, when the weight that the phosphorous-containing polyester of described carboxy blocking accounts for described epoxy resin is 30%, the limiting oxygen index(LOI) of described epoxy resin is raised to 32.9% from 19.8%.
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| CN111087796A (en) * | 2018-10-23 | 2020-05-01 | 今创景新材料科技（上海）有限公司 | Phosphorus-containing copolymerized nylon and preparation method and application thereof |
| CN111087612A (en) * | 2018-10-23 | 2020-05-01 | 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 |
| 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 |
| 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 |
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| 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 |
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| CN104974351B (en) | 2019-05-31 |
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