CN103073728A - Boron-containing polyester, and synthesizing method and applications thereof - Google Patents
Boron-containing polyester, and synthesizing method and applications thereof Download PDFInfo
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- CN103073728A CN103073728A CN2012100927140A CN201210092714A CN103073728A CN 103073728 A CN103073728 A CN 103073728A CN 2012100927140 A CN2012100927140 A CN 2012100927140A CN 201210092714 A CN201210092714 A CN 201210092714A CN 103073728 A CN103073728 A CN 103073728A
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Abstract
The invention relates to the field of polyester, and the synthesizing and applications thereof. The invention discloses a boron-containing polyester with a specific structure represented as the following, wherein n is no smaller than 1. The invention also discloses a synthesizing method of the boron-containing polyester. The method comprises the steps that: raw materials are weighed according to a molar ratio that resorcinol: boric acid=1.0-3.0:1; a feeding reaction is carried out, wherein the materials are added into a reactor, such that resorcinol and boric acid are subjected to a sufficient reaction in the reactor; and a product is obtained, wherein the reaction product after the feeding reaction is discharged, such that the boron-containing polyester is obtained. The invention also discloses applications of the boron-containing polyester: (1) the polyester can be adopted as a curing agent and especially a curing agent of epoxy resin; with the ester, cured resin has fame-retardant performance that the epoxy resin cured product reaches an off-fire extinguishing effect or a short-time extinguishing effect, and he epoxy resin cured product has the properties of no smoke or less smoke; the cured epoxy resin can be applied as an ablation material in an aerospace field, wherein a linear ablation rate is no higher than -0.003mm/s, and mass ablation rate is no higher than 0.086g/s; and (2) the polyester can be applied as a flame retardant, wherein the boron-containing polyester provided by the invention is substantially non-flammable on fire, such that the ester can be directly used as the flame retardant.
Description
Technical field
The present invention relates to the application of a kind of boracic polyester, synthetic method and this polyester thereof.
Background technology
The boron outermost layer only has 3 electronics, is difficult to be made into the state of saturation of 8 electronics when forming compound, thereby sucting electronic effect is arranged; Boron also has the function that absorbs neutron ray, and B-O is strong can be very high.
Resins, epoxy is a kind of chemical substance commonly used in the daily life, generally it is cured rear use.Epoxy resin cured product has following characteristics: (1) mechanical property is high: Resins, epoxy has very strong force of cohesion, and molecular structure is fine and close, so its mechanical property is higher than the universal thermosetting resins such as resol and unsaturated polyester.(2) strong adhesion: contain active greatly epoxy group(ing), hydroxyl and ehter bond, amine key, ester bond isopolarity group in the epoxy resin solidifying system, give the curable epoxide thing to metal, pottery, glass, coagulation scholar, timber isopolarity base material with good sticking power.(3) cure shrinkage is little: be generally 1%～2%, coefficient of linear expansion is also very little, is generally 6 * 10-5/ ℃, so volume change is little after solidifying.(4) good manufacturability: basically do not produce the low molecular weight volatile thing during epoxy resin cure, so but low pressure molding or contact molded; Can cooperate with various solidifying agent environment-friendly type coatings such as making solvent-free, high solid, powder coating and water-borne coatings.(5) good stability, the performance of the mediums such as it is alkaline-resisting, sour, salt corrosion is better than the thermosetting resins such as unsaturated polyester resin, resol, so Resins, epoxy is in a large number as protection against corrosion priming paint; Because epoxy resin cured product is tridimensional network, the dipping of ability oils etc. is widely used in the integral tank inboard wall lining of oil groove, oil tanker, aircraft etc. again again.(6) over-all properties is high behind the curable epoxide, and in a large number for the manufacture of matrix material, it is low to have simultaneously density, and specific tenacity is high, is aerospace field, world today new high-tech material kind with fastest developing speed.
And the Resins, epoxy thermotolerance of amine, anhydride-cured is generally 80～180 ℃ usually, belongs to inflammable articles, and cigarette is large during burning, and toxicity is large, therefore can not satisfy the needs of requirement and the development in Hi-Tech of social development.Therefore, the present invention synthesizes a kind of new boracic polyester in conjunction with the characteristic of boron, and this boracic polyester is applied to solidifying agent field, especially cured epoxy resin.
Summary of the invention
The present invention's the first purpose provides a kind of boracic polyester, and the structural formula of this boracic polyester is as follows:
Wherein n is more than or equal to 1.
Boracic polyester outward appearance red-brown of the present invention, be liquid of vicidity or liquid (being decided by what of dehydrating amount) not under the room temperature, on fire, substantially do not burn, substantially smokeless, wave number is the charateristic avsorption band of B-O key at 1370～1380 peak in its infared spectrum, wave number is the charateristic avsorption band of c h bond in the Resorcinol benzene nucleus 3220 places, has proved that chemical reaction has occured for Resorcinol and boric acid.
The density of boracic polyester of the present invention is at 1.25～1.35g/cm
3The oxygen index of boracic polyester is between 30～38.
The second purpose of the present invention provides the synthetic method of above-mentioned boracic polyester, may further comprise the steps:
(1) takes by weighing raw material: be that 1.0～3.0: 1 ratio row take by weighing by the mol ratio of Resorcinol and boric acid;
(2) charging reaction: the raw material that weighs up in (1) is added in the reactor, allow Resorcinol and boric acid in reactor, fully react;
(3) obtain product: will pour out through (2) reacted reactant, and namely get the boracic polyester.
Described reactor is with thermometer, agitator and condenser;
Described reactor also is furnished with electric control heating arrangement;
The process of described reaction is specially: electric control heating arrangement heats, and when the temperature of the reaction raw materials in the reactor reaches 100～120 ℃, starts agitator and stirs, and open the water coolant of condenser; When treating to have in the condenser water of condensation to ooze, the voltage of electric control heating arrangement control heating makes in the reactor and heats up gradually according to the speed of water of condensation with per minute 0.3g～0.4g; When water of condensation reaches theoretical dehydrating amount 90～100%, termination reaction (calculating take the dehydrating amount of 1 mole of boric acid as 54g).
Preferably, raw material adopts the mode of disposable charging to feed in raw material.
Preferably, electric control heating arrangement is automatically controlled heating heat conduction oil boiler.
The 3rd purpose of the present invention provides the application of boracic polyester of the present invention: (1) as solidifying agent, in particular for cured epoxy resin, the flame retardant properties of epoxy resin cured product can reach the effect of namely going out or namely going out in short-term from fire, and smokeless or low cigarette; The Resins, epoxy of its curing also can be used as the ablator of space industry, and ablation property is (pressing the GJB323A-96 standard testing): linear ablative rate is less than or equal to-0.003mm/ second, and mass ablative rate is less than or equal to 0.086g/ second.And the epoxy linear ablative rate that general amine solidifies is 0.6～0.8mm/s, and mass ablative rate is 0.15～0.2g/s.The epoxy of anhydride-cured, then performance is poorer; (2) as fire retardant: boracic polyester of the present invention itself has substantially incombustible character on fire, therefore, can directly be used as fire retardant.
Description of drawings
Fig. 1 is the infrared spectrum of boracic polyester of the present invention.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing and specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1:
The structural formula of boracic polyester of the present invention is as follows:
Wherein n is more than or equal to 1.
Boracic polyester outward appearance red-brown of the present invention is liquid of vicidity or liquid (being decided by what of dehydrating amount) not under the room temperature, does not substantially burn on fire, and is substantially smokeless.
Fig. 1 is the infrared spectrum of boracic polyester of the present invention, as can be seen from Figure 1, wave number is the charateristic avsorption band of B-O key at 1370～1380 peak, and wave number is the charateristic avsorption band of c h bond in the Resorcinol benzene nucleus 3220 places, therefore, prove that chemical reaction has occured for Resorcinol and boric acid.
The density of boracic polyester of the present invention is at 1.25～1.35g/cm
3The oxygen index of boracic polyester is between 30～38.
The synthetic equation of boracic polyester of the present invention is:
Embodiment 2:
Take by weighing raw material by 1 mole of 1.4 moles of Resorcinol, boric acid, raw material is added in the 500ml there-necked flask, again there-necked flask is put into electric control heating arrangement and heat; Raw material melts gradually in the time of near the material temperature in the there-necked flask reaches 120 ℃, opens agitator and stirs, and opens simultaneously the valve that cooling water flow out of of condenser, allows cooling water flow out of; When the material temperature in the there-necked flask reaches 130 ℃, there is water of condensation to ooze, then slowly regulate the voltage of electric control heating arrangement, make in the there-necked flask and heat up gradually according to the speed of water of condensation with per minute 0.3g, keep continuous condensation and ooze; Until water of condensation reach theoretical dehydrating amount 95% the time, termination reaction; Pour out the reactant in the there-necked flask, namely get the boracic polyester, this boracic polyester is toughness red-brown polymkeric substance.
Get synthetic boracic polyester 50g and put into container, add again polyethers 210#50g, being heated to 60 ℃ mixes well, and then add polyisocyanates 100g, continue to be heated to 80 ℃ and stir, 1 hour～2 hours, react and obtain the polyurethane cured article after complete, this polyurethane cured article has self-extinguishing, extinguishes after 10 seconds from fire, few cigarette.
Embodiment 3:
Take by weighing raw material by 1 mole of 1.5 moles of Resorcinol, boric acid, raw material is added in the 500ml there-necked flask, there-necked flask being put into automatically controlled heating heat conduction oil boiler heats again, raw material melts gradually when the material temperature in the there-necked flask reaches 110 ℃, opening agitator stirs, open simultaneously the cooling water valve of condenser, allow cooling water flow out of; When the material temperature in the there-necked flask reaches 125 ℃, there is water of condensation to ooze, then slowly regulate the voltage of automatically controlled heating heat conduction oil boiler, make in the there-necked flask and heat up gradually according to the speed of water of condensation with per minute 0.4g, keep continuous condensation and ooze; Until water of condensation reach theoretical dehydrating amount 98% the time, termination reaction is poured out the reactant in the there-necked flask, namely gets the boracic polyester, this boracic polyester is toughness red-brown polymkeric substance.
Get synthetic boracic polyester 80g and put into container, add E-51 epoxy 100g, stir, be warming up to 120 ℃ of insulations 2 hours, obtain the curable epoxide thing, this curable epoxide thing has self-extinguishing, and is flammable on fire, leaves flare and puts out in 5～10 seconds.
Embodiment 4:
Take by weighing raw material according to 1.1 moles of 1.5 moles of Resorcinols, boric acid, raw material is added in the 500ml there-necked flask, there-necked flask being put into automatically controlled heating heat conduction oil boiler heats again, raw material melts gradually when the material temperature in the there-necked flask reaches 120 ℃, opening agitator stirs, open simultaneously the cooling water valve of condenser, allow cooling water flow out of; When the material temperature in the there-necked flask reaches 132 ℃, there is water of condensation to ooze, then slowly regulate the voltage of automatically controlled heating heat conduction oil boiler, make in the there-necked flask and heat up gradually according to the speed of water of condensation with per minute 0.3g, keep continuous water of condensation and ooze; Until water of condensation reach theoretical dehydrating amount 100% near the time, termination reaction is poured out the reactant in the there-necked flask, namely gets the boracic polyester, this boracic polyester is toughness red-brown polymkeric substance.
To get synthetic boracic polyester 20g and put into container, add tetrafunctional epoxy resin 20g, mix well, be warming up to again 120 ℃ and keep 1h, pour out, obtain epoxy resin cured product, its linear ablative rate is-0.003mm/ second, mass ablative rate is 0.086g/ second.
More than technical scheme that the embodiment of the invention is provided be described in detail, used specific case herein principle and the embodiment of the embodiment of the invention are set forth, the explanation of above embodiment is only applicable to help to understand the principle of the embodiment of the invention; Simultaneously, for one of ordinary skill in the art, according to the embodiment of the invention, all will change on embodiment and range of application, in sum, this description should not be construed as limitation of the present invention.
Claims (8)
1. boracic polyester is characterized in that having following structural formula:
Wherein n is more than or equal to 1.
2. synthetic method of boracic polyester as claimed in claim 1 is characterized in that may further comprise the steps:
(1) takes by weighing raw material: be that 1.0～3.0: 1 ratio row take by weighing by the mol ratio of Resorcinol and boric acid;
(2) charging reaction: the raw material that weighs up in (1) is added in the reactor, allow Resorcinol and boric acid in reactor, fully react;
(3) obtain product: will pour out through (2) reacted reactant, and namely get the boracic polyester.
Described reactor is with thermometer, agitator and condenser;
Described reactor also is furnished with electric control heating arrangement;
The process of described reaction is specially: electric control heating arrangement heats, and when the temperature of the reaction raw materials in the reactor reaches 100～120 ℃, starts agitator and stirs, and open the water coolant of condenser; When treating to have in the condenser water of condensation to ooze, the voltage of electric control heating arrangement control heating makes in the reactor and heats up gradually according to the speed of water of condensation with per minute 0.3g～0.4g; When water of condensation reaches theoretical dehydrating amount 90～100%, termination reaction (calculating take the dehydrating amount of 1 mole of boric acid as 54g).
3. the synthetic method of described boracic polyester according to claim 2 is characterized in that described raw material adopts the mode of disposable charging to feed in raw material.
4. the synthetic method of described boracic polyester according to claim 2 is characterized in that described electric control heating arrangement is automatically controlled heating heat conduction oil boiler.
5. as claimed in claim 1 application of boracic polyester is characterized in that described boracic polyester is as solidifying agent.
6. the according to claim 5 application of described boracic polyester is characterized in that described boracic polyester is as epoxy curing agent.
7. the according to claim 6 application of described boracic polyester is characterized in that Resins, epoxy behind the described boracic curable polyester is as the ablator of space industry.
8. as claimed in claim 1 application of boracic polyester is characterized in that described boracic polyester is as fire retardant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100927140A CN103073728A (en) | 2012-04-01 | 2012-04-01 | Boron-containing polyester, and synthesizing method and applications thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100927140A CN103073728A (en) | 2012-04-01 | 2012-04-01 | Boron-containing polyester, and synthesizing method and applications thereof |
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| CN103073728A true CN103073728A (en) | 2013-05-01 |
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| CN2012100927140A Pending CN103073728A (en) | 2012-04-01 | 2012-04-01 | Boron-containing polyester, and synthesizing method and applications thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056842A (en) * | 2015-07-23 | 2015-11-18 | 厦门大学 | Reaction apparatus and application thereof in synthesizing borate |
| CN108690510A (en) * | 2018-07-01 | 2018-10-23 | 张玲 | A kind of preparation method of leather gloss agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1902005A (en) * | 1932-03-12 | 1933-03-21 | Du Pont | Preservation of rubber |
| US4655948A (en) * | 1985-08-27 | 1987-04-07 | Mobil Oil Corporation | Grease compositions containing borated catechol compounds and hydroxy-containing soap thickeners |
| US4781850A (en) * | 1985-08-27 | 1988-11-01 | Mobil Oil Corporation | Grease compositions containing borated catechol compounds and hydroxy-containing soap thickeners |
| CN101041718A (en) * | 2007-04-27 | 2007-09-26 | 西安交通大学 | Preparation method for hyper branched boric acid ester |
-
2012
- 2012-04-01 CN CN2012100927140A patent/CN103073728A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1902005A (en) * | 1932-03-12 | 1933-03-21 | Du Pont | Preservation of rubber |
| US4655948A (en) * | 1985-08-27 | 1987-04-07 | Mobil Oil Corporation | Grease compositions containing borated catechol compounds and hydroxy-containing soap thickeners |
| US4781850A (en) * | 1985-08-27 | 1988-11-01 | Mobil Oil Corporation | Grease compositions containing borated catechol compounds and hydroxy-containing soap thickeners |
| CN101041718A (en) * | 2007-04-27 | 2007-09-26 | 西安交通大学 | Preparation method for hyper branched boric acid ester |
Non-Patent Citations (1)
| Title |
|---|
| 刘育红: "超支化硼酸酯改性酚醛树脂的高性能化研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 01, 15 January 2012 (2012-01-15) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056842A (en) * | 2015-07-23 | 2015-11-18 | 厦门大学 | Reaction apparatus and application thereof in synthesizing borate |
| CN108690510A (en) * | 2018-07-01 | 2018-10-23 | 张玲 | A kind of preparation method of leather gloss agent |
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Application publication date: 20130501 |