CN113045741B - Phosphorus-containing carboxyl-terminated hyperbranched polyester, preparation method thereof, phosphorus-containing hyperbranched epoxy resin, preparation method thereof and application thereof - Google Patents
Phosphorus-containing carboxyl-terminated hyperbranched polyester, preparation method thereof, phosphorus-containing hyperbranched epoxy resin, preparation method thereof and application thereof Download PDFInfo
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Abstract
The invention provides a hyperbranched polyester containing phosphorus-terminated carboxyl groups and a hyperbranched epoxy resin containing phosphorus; the application also provides application of the phosphorus-containing hyperbranched epoxy resin in epoxy prepregs, modified cyanate esters and cyanate ester prepregs. The hyperbranched epoxy resin is used for the prepreg, can improve the flame retardance and mechanical property of the prepreg, is used for modifying cyanate ester, can obtain the low-dielectric-property, low-loss, high-temperature-resistant and flame-retardant cyanate ester resin, can ensure the performance advantage of the cyanate ester resin, and can also improve the mechanical property and flame retardance.
Description
Technical Field
The invention relates to the technical field of materials, in particular to phosphorus-containing carboxyl-terminated hyperbranched polyester, a preparation method thereof, phosphorus-containing hyperbranched epoxy resin, a preparation method thereof and application thereof.
Background
At present, research reports on the obvious reinforcing and toughening effects of hyperbranched polymers exist in domestic and foreign documents, but the hyperbranched polymers have no flame retardant function.
Organic high molecular polymers are mostly inflammable materials (such as epoxy resins, cyanate resins), which limit the field of application. In practical applications, flame retardants are generally added to solve the above problems, for example, flame retardants containing phosphorus, halogen, inorganic metals and the like are added, the method for adding the flame retardants is simple and low in cost, but other performances of the system are also reduced along with the addition of small molecular flame retardants, such as heat resistance, mechanical properties and electrical properties; in addition, the flame-retardant elements such as phosphorus, nitrogen, silicon and the like are directly introduced into polymer molecules, so that a good flame-retardant effect is achieved on the premise of not affecting mechanical properties. As an important epoxy resin and hyperbranched polymer, the hyperbranched epoxy resin has a series of unique physicochemical characteristics of low viscosity, easy film formation, high activity, easy functionalization and the like, so that the hyperbranched epoxy resin has wide application in a plurality of fields: the hyperbranched epoxy resin can be used as an epoxy toughening agent, a functional adhesive, a functional energy type coating resin and the like.
On the other hand, the cyanate resin is a high-performance thermosetting resin, and the cured cyanate resin has lower dielectric constant (2.8-3.2), extremely small dielectric loss tangent (0.002-0.008), high glass transition temperature (240-290 ℃), low shrinkage, low moisture absorption (less than 1.5%), excellent mechanical property and adhesive property, and good processing manufacturability, and is widely applied to high-frequency high-speed circuit boards, high-performance wave-transparent materials and high-performance structural composite material resin matrixes for aerospace. The cyanate has the defects of poor curing manufacturability and large brittleness of a cured product, and in a system without a catalyst, the cyanate needs to be cured for a long time at the curing temperature of more than 200 ℃ so that the curing degree can reach more than 90%; when the catalyst system is used for curing, the mechanical property and hygroscopicity of the resin system can be reduced, so that the application field is limited. In the modification of the cyanate resin, the addition of a high-performance thermosetting resin, thermoplastic resin, or the like can improve the toughening effect, but can reduce the heat resistance and modulus of the resin.
Disclosure of Invention
The invention solves the technical problem of providing the phosphorus-containing carboxyl-terminated hyperbranched polyester, the phosphorus-containing hyperbranched epoxy resin, the modified cyanate and the prepreg, wherein the phosphorus-containing carboxyl-terminated hyperbranched polyester and the phosphorus-containing hyperbranched epoxy resin have excellent toughening effect and flame retardance, and the toughness, tensile strength, bending strength and flame retardance of the resin composition and the prepreg can be improved by using the hyperbranched polymer in the resin composition and the prepreg.
In view of this, the present application provides a phosphorus-containing carboxyl-terminated hyperbranched polyester obtained by esterification polymerization of tricarboxyethyl phosphine and a glycol.
Preferably, the molar ratio of the tricarboxyethyl phosphine to the dihydric alcohol is (n+1): n, wherein n is more than or equal to 3.
The application also provides a preparation method of the phosphorus-containing carboxyl end hyperbranched polyester, which comprises the following steps:
reacting tricarboxyethyl phosphine, dihydric alcohol and a catalyst in a solvent to obtain hyperbranched polyester containing phosphorus end carboxyl groups, wherein the catalyst is one or more selected from tetrabutyl titanate, p-toluenesulfonic acid, zinc acetate, sulfuric acid, phosphoric acid and tetrapropyl titanate, and the dosage of the catalyst is 0.3-1wt% of the total amount of the tricarboxyethyl phosphine and the dihydric alcohol; the reaction is carried out in a protective atmosphere, the temperature of the reaction is 100-200 ℃, and the reaction time is 1-10 h.
The application also provides the phosphorus-containing hyperbranched epoxy resin, which is prepared by reacting the phosphorus-containing carboxyl-terminated hyperbranched polyester prepared by the preparation method with epichlorohydrin.
The application also provides application of the phosphorus-containing hyperbranched epoxy resin in a resin composition and/or a fiber reinforced material.
The application also provides an epoxy prepreg, which comprises a fiber reinforced material and the phosphorus-containing hyperbranched epoxy resin.
Preferably, the epoxy resin prepreg is composed of epoxy resin, fiber reinforced material and phosphorus-containing hyperbranched epoxy resin, wherein the phosphorus-containing hyperbranched epoxy resin accounts for 5-10wt% of the epoxy resin, and the phosphorus-containing hyperbranched epoxy resin accounts for 30-70wt% of the fiber reinforced material.
The application also provides a modified cyanate resin, which comprises, by mass, 100 parts of bisphenol type cyanate, 3-10 parts of toughening resin, 2-10 parts of epoxy resin, 0.5-10 parts of phosphorus-containing hyperbranched epoxy resin, 3-10 parts of flame retardant and 0.5-2 parts of coupling agent.
The application also provides a cyanate ester prepreg which consists of the modified cyanate ester resin and a fiber reinforced material.
Preferably, the modified cyanate resin is 30 to 50wt% of the cyanate ester prepreg.
The application provides a hyperbranched polyester containing phosphorus end carboxyl groups and a hyperbranched epoxy resin containing phosphorus; the hyperbranched epoxy resin provided by the application is used for the prepreg, and can improve the flame retardance and the mechanical property of the prepreg; meanwhile, the hyperbranched epoxy resin is used for modifying cyanate, the high-activity epoxy groups in the hyperbranched epoxy resin can react with cyanate active groups to generate oxazolidine five-membered rings, so that the crosslinking density of triazine rings generated by curing the cyanate is reduced, meanwhile, the three-dimensional spherical structure, high fluidity and high-activity end groups of the hyperbranched epoxy resin form a mutual transmission network structure in the curing process, and the toughness and strength of the cured resin are improved; therefore, the low-dielectric, low-loss, high-temperature-resistant and flame-retardant cyanate resin can be obtained, the performance advantage of the cyanate resin can be ensured, and the mechanical property and flame retardance can be improved.
On the other hand, the phosphorus-containing hyperbranched epoxy resin can change the defect that a metal salt catalyst is added into the current cyanate resin, and the hyperbranched epoxy resin contains a small amount of hydroxyl groups, can react with cyanate ester monomers to generate iminocarbonic acid diester, and then generate oxazine rings with cyanate ester groups, so that three-way network macromolecules are generated at last in a circulating way, and the overall reaction is catalyzed, so that the reaction can be accelerated, and the high-temperature wet heat performance of the resin can be ensured.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The embodiment of the invention discloses phosphorus-containing carboxyl-terminated hyperbranched polyester, which is prepared by esterification polymerization of tricarboxyethyl phosphine and dihydric alcohol.
In the application, the phosphorus-containing carboxyl-terminated hyperbranched polyester is obtained by esterification polymerization of tricarboxyethyl phosphine and dihydric alcohol; specifically, the phosphorus-containing carboxyl end hyperbranched polyester can be represented by the following formula (I):
wherein m is more than or equal to 3;
the above-mentioned hyperbranched polyester containing phosphorus end carboxyl groups is obtained by esterification polymerization, and the specific structure of P varies with the reaction raw materials and the reaction conditions, but the carboxyl groups therein can be determined according to the raw materials. Preferably, m is greater than or equal to 6 in the above-mentioned phosphorus-containing carboxyl end hyperbranched polyester, which can ensure that the polymer has a hyperbranched structure and a plurality of active reaction points, the structure of the phosphorus-containing carboxyl end hyperbranched polyester can be shown as the following formula, but the structure of the phosphorus-containing carboxyl end hyperbranched polyester is not limited to this, and the phosphorus-containing carboxyl end hyperbranched polyester can be selected from the group consisting of the compounds shown as the formula (I) 1 ) A process for preparing (I) 2 ) A process for preparing (I) 3 ) And (I) 4 ) One or more of the following;
wherein R is 1 Is that
；R 2 Is->
。
In the above specific structural formula, R is different according to the diol usedThe diol is a diol well known to those skilled in the art, and there is no particular limitation in this application, and the R may be selected from the group consisting of-OCH 2 CH 2 OCH 2 CH 2 O-、-OCH 2 CH 2 CH 2 CH 2 O-、-OCH 2 CH 2 O-、-OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 O-、
Or (b)
The structural formula of the phosphorus-containing carboxyl-terminated hyperbranched polyester is shown as a formula (I), wherein P is a hyperbranched structure, and in some specific embodiments, the phosphorus-containing carboxyl-terminated hyperbranched polyester is marked as HPAC-n; n=1, m may correspond to 6, representing a first generation of carboxyl terminated hyperbranched polymer; n=2, m may correspond to 12, representing a second generation carboxyl-terminated hyperbranched polymer; n=3, m may correspond to 24, representing a third generation carboxyl-terminated hyperbranched polymer; n=4, m may correspond to 48, representing a fourth generation carboxyl-terminated hyperbranched polymer. Specifically, when the molar ratio of the tricarboxyethyl phosphine to the dihydric alcohol is about 4:3, HPAC-1 can be obtained; HPAC-2 can be obtained when the mol ratio of the tricarboxyethyl phosphine to the dihydric alcohol is about 10:9; HPAC-3 can be obtained when the mol ratio of the tricarboxyethyl phosphine to the dihydric alcohol is about 22:21; HPAC-4 is obtained at a molar ratio of tricarboxyethyl phosphine to diol of about 46:45. The application also provides a preparation method of the phosphorus-containing carboxyl end hyperbranched polyester, which comprises the following steps:
and (3) reacting tricarboxylethyl phosphine, dihydric alcohol and a catalyst in a solvent to obtain the phosphorus-containing carboxyl-terminated hyperbranched polyester.
In the process of preparing the phosphorus-containing carboxyl end hyperbranched polyester, the catalyst is one or more selected from tetrabutyl titanate, p-toluenesulfonic acid, zinc acetate, sulfuric acid, phosphoric acid and tetrapropyl titanate, and the dosage of the catalyst is 0.3-1wt% of the total weight of the tricarboxyethyl phosphine and the dihydric alcohol. The solvent is an organic solvent well known to those skilled in the art, and there is no particular limitation in this application, and in a specific embodiment, the solvent is xylene. The reaction is carried out in a nitrogen protection atmosphere, the temperature of the reaction is 100-200 ℃, the time is 1-10 h, and in a specific embodiment, the temperature of the reaction is 150-160 ℃ and the time is 4-6 h. The diols are well known to those skilled in the art, and the present application is not particularly limited. In specific embodiments, the glycol may be selected from ethylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 2-butanediol, or 1, 2-propanediol.
The application also provides a phosphorus-containing hyperbranched epoxy resin, which is obtained by reacting the phosphorus-containing carboxyl-terminated hyperbranched polyester and epichlorohydrin.
The phosphorus-containing hyperbranched epoxy resin is prepared from phosphorus-containing carboxyl-terminated hyperbranched polyester and epichlorohydrin, and is specifically shown as a formula (II):
wherein m is more than or equal to 6;
s is a natural number of 1 to 5.
The hyperbranched structural formula of the hyperbranched polyester containing the phosphorus end carboxyl groups corresponds to the hyperbranched structure of the hyperbranched epoxy resin containing the phosphorus, and after the hyperbranched structural formula of the hyperbranched polyester containing the phosphorus end carboxyl groups is determined, the hyperbranched structural formula of the hyperbranched epoxy resin containing the phosphorus can also be determined. In some embodiments, the hyperbranched epoxy resins described herein can be labeled HPEP-n, again, n is 1,2, 3, or 4, respectively, and then m can correspond to 6, 12, 24, or 48.
The application also provides a preparation method of the phosphorus-containing hyperbranched epoxy resin, which comprises the following steps:
and (3) reacting the phosphorus-containing hyperbranched polyester, epoxy chloropropane and an alkaline catalyst in an organic solvent to obtain the phosphorus-containing hyperbranched epoxy resin.
In the process of preparing the phosphorus-containing hyperbranched epoxy resin, the molar ratio of carboxyl in the phosphorus-containing hyperbranched epoxy resin to the epichlorohydrin is 1: (1.5-5); the alkaline catalyst can be specifically selected from sodium hydroxide solution with the concentration of 30-40 wt%; the molar ratio of the epichlorohydrin to the sodium hydroxide in the sodium hydroxide solution is 1 (0.5-1.5). The organic solvent is a solvent well known to those skilled in the art, and there is no particular limitation in this application, and the organic solvent may be exemplified by one or more of toluene, xylene, tetrahydrofuran, ethyl acetate, propyl acetate, butyl acetate, and dioxane.
The reaction formula for preparing the phosphorus-containing carboxyl-terminated hyperbranched polyester and the phosphorus-containing hyperbranched epoxy resin is shown as follows:
the invention provides a hyperbranched polyester containing phosphorus end carboxyl, which is synthesized by a one-step method, and then the hyperbranched polyester containing phosphorus is prepared by reacting with epichlorohydrin, so that the ring closure rate is high, and the method is simple; the obtained phosphorus-containing hyperbranched polyester and phosphorus-containing hyperbranched epoxy resin have excellent toughening effect and flame retardance, and can effectively improve the toughness, tensile strength, bending strength and flame retardance of the epoxy resin.
The application also discloses application of the phosphorus-containing hyperbranched epoxy resin or the phosphorus-containing hyperbranched epoxy resin in a resin composition and/or a fiber reinforced material.
The application also provides an epoxy prepreg which comprises the fiber reinforced material and the phosphorus-containing hyperbranched epoxy resin. In some embodiments, the epoxy prepreg may be composed of an epoxy resin, a fiber reinforcement, and the above-described phosphorous hyperbranched epoxy resin.
The epoxy prepreg is only one specific application of the phosphorus-containing hyperbranched epoxy resin, and the phosphorus-containing hyperbranched epoxy resin is specifically applied to the epoxy prepreg. Specifically, the epoxy prepreg is prepared from epoxy resin, fiber reinforced material and phosphorus-containing hyperbranched epoxy resin; more specifically, the phosphorus-containing hyperbranched epoxy resin accounts for 5-10wt% of the epoxy resin, and the phosphorus-containing hyperbranched epoxy resin accounts for 30-70wt% of the fiber reinforced material.
In the epoxy prepreg, the epoxy resin is well known to those skilled in the art, and more specifically, may be selected from an EM103 medium temperature curing epoxy resin, and may also be selected from YPH-160 (Kunshan Yubo composite New Material Co., ltd.), WP-S3001 (Hui Bai New material) and the like. The fiber reinforced material is a fiber reinforced material well known to those skilled in the art, and can be specifically selected from glass fiber, quartz fiber, aramid fiber, ultra-high molecular weight polyethylene, basalt fiber, and the like.
The method for preparing the epoxy prepreg according to the present application may be carried out according to methods well known to those skilled in the art, and is not particularly limited thereto; in a specific embodiment, the method is as follows: and mixing the phosphorus-containing hyperbranched epoxy resin and the epoxy resin, and then carrying out impregnation with the fiber reinforced material after film formation to obtain the epoxy prepreg.
The invention also provides application of the phosphorus-containing hyperbranched epoxy resin to modified cyanate resin, namely the modified cyanate resin is prepared from bisphenol type cyanate, toughening resin, liquid epoxy resin, flame retardant, silane coupling agent and the phosphorus-containing hyperbranched epoxy resin.
The modified cyanate resin provided by the application can obtain low-dielectric, low-loss, high-temperature-resistant and flame-retardant cyanate without a catalyst. Specifically, the content of bisphenol cyanate in the modified cyanate resin is 100 parts by weight, the content of the toughening resin is 3-10 parts by weight, the content of the liquid epoxy resin is 2-10 parts by weight, the content of the phosphorus-containing hyperbranched epoxy resin is 0.5-10 parts by weight, the content of the flame retardant is 3-10 parts by weight, and the content of the silane coupling agent is 0.5-2 parts by weight; in a specific embodiment, the content of the toughening resin is 5-8 parts by weight, the content of the liquid epoxy resin is 2-5 parts by weight, the content of the phosphorus-containing hyperbranched epoxy resin is 1-5 parts by weight, the content of the flame retardant is 4-8 parts by weight, and the content of the silane coupling agent is 0.5-1 part by weight.
In the modified cyanate ester of the present invention, the bisphenol type cyanate ester, the toughening resin, the liquid epoxy resin, the flame retardant and the silane coupling agent are all well known to those skilled in the art, and the specific selection thereof is not particularly limited in the present application; illustratively, the bisphenol type cyanate is selected from one or two of bisphenol A type cyanate, bisphenol M type cyanate, bisphenol F type cyanate and bisphenol S type cyanate; the toughening resin is selected from one or more of polysulfone, polyether sulfone, polyether imide, polyether ether ketone, polyphenyl ether and polyphenyleneoxide resin; the liquid epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, phenolic epoxy resin and bisphenol E cyanate; the silane coupling agent is one or two selected from gamma-glycidoxypropyl trimethoxysilane and gamma-aminopropyl trimethoxysilane.
The method for modifying the cyanate ester is carried out according to the method well known by the person skilled in the art, namely, bisphenol type cyanate ester is heated and melted, then toughening resin, liquid epoxy resin, phosphorus-containing hyperbranched epoxy resin, flame retardant and silane coupling agent are added, and the modified cyanate ester is obtained after reaction.
After providing a modified cyanate ester resin, the present application also provides a cyanate ester prepreg prepared from the modified cyanate ester resin and a fiber reinforcement material.
In a specific embodiment, the modified cyanate ester resin is 30 to 50 weight percent of the cyanate ester prepreg. The fiber reinforced material is selected from one or more of glass fiber, quartz fiber, aramid fiber, ultra-high molecular weight polyethylene and basalt fiber.
The cyanate ester prepreg is prepared according to a preparation method well known to a person skilled in the art, namely, the cyanate ester prepreg is obtained by impregnating the cyanate ester resin with a fiber reinforced material after the cyanate ester resin is formed into a film.
In order to further understand the present invention, the hyperbranched epoxy resin provided by the present invention and the application thereof will be described in detail with reference to examples, and the scope of the present invention is not limited by the following examples.
In the following examples, the viscosity is measured by a rotary viscometer, and the epoxy value is measured by an acetone hydrochloride method (according to national standard GB 1677);
the quartz fiber adopts Wuhan Xinyou Yongtai (thickness 0.10mm; surface density 95+ -10 g/m) 2 )。
Example 1
1) Adding 1mol of tricarboxyethyl phosphine (TCEPO), 0.9mol of diethylene glycol (DEG), 1.73g of p-toluenesulfonic acid and 300ml of dimethylbenzene into a three-neck flask of a water separator, a condenser tube, a thermometer and a stirrer, heating to 155 ℃ under the protection of nitrogen, reacting for 6 hours, and removing the dimethylbenzene after the reaction is finished to obtain second-generation phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester;
2) Adding 0.1mol of the prepared phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester and 3.6mol of Epoxy Chloropropane (ECH) into a three-neck reaction flask, reacting for 2 hours at 100-115 ℃, and steaming out excessive ECH after the reaction is finished; adding an organic solvent for full dissolution, slowly dropwise adding 4.8mol of 40wt% sodium hydroxide aqueous solution at room temperature, reacting for 5 hours, washing with water for three times after the reaction is finished, and removing the organic solvent to obtain light yellow second-generation phosphorus-containing hyperbranched epoxy resin; the viscosity was 1100cp at 25℃and the epoxy value was 0.17mol/100g.
3) Preparation of flame-retardant epoxy prepreg: mixing the prepared phosphorus-containing flame-retardant hyperbranched epoxy resin with the EM103 medium-temperature cured epoxy resin, wherein the phosphorus-containing flame-retardant hyperbranched epoxy resin accounts for 5% of the mass of the EM 103; then preparing flame-retardant epoxy prepreg by using a prepreg production line two-step method, wherein the surface density of quartz fiber is 95g/m 2 Resin content 43% + -3, prepreg areal density 150+ -10 g/m 2 。
Example 2
1) Adding 2.2mol of tricarboxylethyl phosphine (TCEPO), 2.1mol of diethylene glycol (DEG), 3.86g of p-toluenesulfonic acid and 400ml of dimethylbenzene into a three-neck flask of a water separator, a condenser tube, a thermometer and a stirrer, heating to 160 ℃ under the protection of nitrogen, reacting for 6 hours, and removing the dimethylbenzene after the reaction is finished to obtain the third-generation phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester;
2) Adding 0.1mol of the prepared third-generation phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester and 4.8mol of Epoxy Chloropropane (ECH) into a three-neck reaction flask, reacting for 2 hours at 100-115 ℃, and evaporating excessive ECH after the reaction; adding an organic solvent for full dissolution, slowly dropwise adding 5.2mol of 45wt% sodium hydroxide aqueous solution at room temperature, reacting for 5 hours, washing with water for three times after the reaction is finished, and removing the organic solvent to obtain light yellow third-generation phosphorus-containing hyperbranched epoxy resin; the test viscosity at 25℃was 1400cp and the epoxy value was 0.15mol/100g.
3) Mixing the prepared phosphorus-containing flame-retardant hyperbranched epoxy resin with the EM103 medium-temperature cured epoxy resin, wherein the phosphorus-containing flame-retardant hyperbranched epoxy resin accounts for 8% of the mass of the EM 103; then preparing flame-retardant epoxy prepreg by using a prepreg production line two-step method, wherein the fiber surface density is 95g/m 2 Resin content 43% + -3, prepreg areal density 150+ -10 g/m 2 。
Example 3
1) Adding 2.3mol of tricarboxylethyl phosphine (TCEPO), 2.25mol of diethylene glycol (DEG), 5.69g of p-toluenesulfonic acid and 450ml of dimethylbenzene into a three-neck flask of a water separator, a condenser tube, a thermometer and a stirrer, heating to 160 ℃ under the protection of nitrogen, reacting for 6 hours, and removing the dimethylbenzene after the reaction is finished to obtain fourth-generation phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester;
2) Adding 0.1mol of the prepared fourth-generation phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester and 12mol of Epoxy Chloropropane (ECH) into a three-neck reaction flask, reacting for 2 hours at 100-115 ℃, and evaporating excessive ECH after the reaction is finished; adding an organic solvent for full dissolution, slowly dropwise adding 14.4mol of 45wt% sodium hydroxide aqueous solution at room temperature, reacting for 5 hours, washing with water for three times after the reaction is finished, and removing the organic solvent to obtain light yellow fourth-generation phosphorus-containing hyperbranched epoxy resin; the test viscosity at 25℃was 1620cp and the epoxy value was 0.16mol/100g.
3) Mixing the prepared phosphorus-containing flame-retardant hyperbranched epoxy resin with the EM103 medium-temperature cured epoxy resin, wherein the phosphorus-containing flame-retardant epoxy resinHyperbranched epoxy resin accounts for 8% of the mass of EM 103; then preparing flame-retardant epoxy prepreg by using a prepreg production line two-step method, wherein the fiber surface density is 95g/m 2 Resin content 43% + -3, prepreg areal density 150+ -10 g/m 2 。
Example 4
1) Adding 1mol of tricarboxyethyl phosphine (TCEPO), 0.9mol of ethylene glycol, 2.14g of p-toluenesulfonic acid and 300ml of dimethylbenzene into a three-neck flask of a water separator, a condenser tube, a thermometer and a stirrer, heating to 160 ℃ under the protection of nitrogen, reacting for 6 hours, and removing the dimethylbenzene after the reaction is finished to obtain second-generation phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester;
2) Adding 0.1mol of the prepared phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester and 3.6mol of Epoxy Chloropropane (ECH) into a three-neck reaction flask, reacting for 2 hours at 100-115 ℃, and steaming out excessive ECH after the reaction is finished; adding an organic solvent for full dissolution, slowly dropwise adding 4.8mol of 45wt% sodium hydroxide aqueous solution at room temperature, reacting for 5 hours, washing with water for three times after the reaction is finished, and removing the organic solvent to obtain the light yellow second-generation phosphorus-containing hyperbranched epoxy resin, wherein the test viscosity is 1200cp at 25 ℃, and the epoxy value is 0.16mol/100g.
3) Mixing the prepared phosphorus-containing flame-retardant hyperbranched epoxy resin with the EM103 medium-temperature cured epoxy resin, wherein the phosphorus-containing flame-retardant hyperbranched epoxy resin accounts for 10% of the mass of the EM 103; then preparing flame-retardant epoxy prepreg by using a prepreg production line two-step method, wherein the surface density of quartz fiber is 95g/m 2 Resin content 43% + -3, prepreg areal density 150+ -10 g/m 2 。
Example 5
1) Adding 1mol of tricarboxyethyl phosphine (TCEPO), 0.9mol of triethylene glycol, 1.93g of p-toluenesulfonic acid and 300ml of dimethylbenzene into a three-neck flask of a water knockout vessel, a condenser tube, a thermometer and a stirrer, heating to 160 ℃ under the protection of nitrogen, reacting for 6 hours, and removing the dimethylbenzene after the reaction is finished to obtain second-generation phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester;
2) Adding 0.1mol of the prepared phosphorus-containing flame-retardant carboxyl-terminated hyperbranched polyester and 2.4mol of Epoxy Chloropropane (ECH) into a three-neck reaction flask, reacting for 2 hours at 100-115 ℃, and steaming out excessive ECH after the reaction is finished; adding an organic solvent for full dissolution, slowly dropwise adding 2.4mol of 45wt% sodium hydroxide aqueous solution at room temperature, reacting for 5 hours, washing with water for three times after the reaction is finished, and removing the organic solvent to obtain light yellow second-generation phosphorus-containing hyperbranched epoxy resin; the test viscosity at 25℃was 1050cp and the epoxy value was 0.16mol/100g.
3) Mixing the prepared phosphorus-containing flame-retardant hyperbranched epoxy resin with the EM103 medium-temperature cured epoxy resin, wherein the phosphorus-containing flame-retardant hyperbranched epoxy resin accounts for 10% of the mass of the EM 103; then preparing flame-retardant epoxy prepreg by using a prepreg production line two-step method, wherein the surface density of quartz fiber is 95g/m 2 Resin content 43% + -3, prepreg areal density 150+ -10 g/m 2 。
Comparative example 1
Mixing EM103 medium-temperature cured epoxy resin with 15 parts by mass of ammonium polyphosphate, and preparing flame-retardant epoxy prepreg by using a prepreg production line two-step method, wherein the surface density of quartz fiber is 95g/m 2 Resin content 43% + -3, prepreg areal density 150+ -10 g/m 2 。
Comparative example 2
Preparing epoxy prepreg by using EM103 epoxy resin and using a prepreg production line two-step method, wherein the surface density of quartz fiber is 95g/m 2 Resin content 43% + -3, prepreg areal density 150+ -10 g/m 2 。
The epoxy prepregs prepared in the above examples and comparative examples were laid up separately, and cured at 100 ℃ for 60min+135 ℃/120min using a vacuum bagging process to obtain laminates.
The tensile properties of the laminates were tested according to ASTM D3039; the compression properties of the laminates were tested according to ASTM D6641/D6641M-01 standard; the in-plane shear properties of the laminates were tested according to ASTM D4255/D4255-01 standard; the glass transition temperature of the laminate was tested according to ASTM D7028-07; performing a flame retardant performance test according to a test standard specified by UL-94; the results are shown in Table 1:
table 1 table of performance data for laminates
By adding the hyperbranched epoxy resin, the flame retardant property of the prepreg is obviously improved, compared with the prepreg added with the flame retardant, the mechanical property is not reduced, but is improved by about 10%, and the glass transition is not reduced.
Examples 6 to 9 preparation of modified cyanate resins and prepregs
1) Preparation of modified cyanate resin: heating 100 parts of bisphenol cyanate monomer to 130 ℃ for melting, adding 3-10 parts of toughening resin under stirring, after the solution is completed, continuously adding 2-5 parts of liquid epoxy resin, 0.5-5 parts of phosphorus-containing flame retardant hyperbranched epoxy prepared in the embodiment, 3-10 parts of flame retardant and 0.5-2 parts of silane coupling agent, continuously reacting at 140-145 ℃ until the viscosity is 7000-12000 cp (100 ℃), stopping heating, and naturally cooling to room temperature to obtain high-performance flame retardant cyanate resin;
the preparation methods of comparative examples 3 and 4 were the same as described above, except that the raw materials were different, and specific raw materials of specific examples 6 to 10 and comparative examples 3 to 4 were selected as shown in Table 2;
wherein: the bisphenol type cyanate comprises: one or two of bisphenol A type cyanate (CY-1, industrial product, jiangsu City Wu Qiao resin factory), bisphenol M type cyanate, bisphenol F type cyanate and bisphenol S type cyanate;
the toughening resin is thermoplastic resin, and comprises: polysulfone (preferably one or more of intrinsic viscosity 0.59-0.64), polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene oxide and polyphenylene oxide resin;
the liquid epoxy resin comprises one or a mixture of bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, phenolic epoxy resin and bisphenol E cyanate;
the silane coupling agent is one or two of gamma-glycidoxypropyl trimethoxy silane and gamma-aminopropyl trimethoxy silane.
2. Preparation of flame-retardant cyanate ester prepreg flame-retardant cyanate ester resin is firstly subjected to film coating machine at 75 ℃ to obtain the surface density of 31+/-3 g/m 2 Adhesive film, then on an impregnating machine at 90℃with a quartz fiber cloth (areal density 94g/m 2 ) The flame-retardant cyanate quartz fiber prepreg (resin content 40%) is obtained by the double-sided impregnation process, and the surface density is 165+/-5 g/m 2 。
Table 2 specific raw material data tables for examples 6 to 9 and comparative examples 3 to 4
The flame-retardant cyanate ester quartz fiber prepreg prepared according to the table above is cured according to 140 ℃/2h+190 ℃/2h by adopting a vacuum bagging process, and a laminated board is obtained.
Gel time of the resin was measured according to the third part wiredrawing method specified in HB 7736.7-2004 at 180+ -1deg.C; testing the radial tensile properties of the laminate according to ASTM D3039 at room temperature ambient RTD; the laminates were tested for radial compression performance according to ASTM D6641/D6641M-01; the in-plane shear properties of the laminates were tested according to ASTM D4255/D4255-01 standard; the glass transition temperature of the laminate was tested according to ASTM D7028-07; performing a flame retardant performance test according to a test standard specified by UL-94; testing the dielectric property of 10GHz by adopting an AET method; the radial tensile properties of the laminates were tested in a high temperature wet environment ETW (test specimens were subjected to moisture absorption equilibrium at (70±3) °c and (85±3)% RH relative humidity) and then tested at (135±3) °c). The results are shown in Table 3;
table 3 table of performance data of laminates prepared in examples 6 to 10 and comparative examples 3 to 4
The cyanate resin modified by the phosphorus-containing hyperbranched epoxy resin has good manufacturability and obviously reduced curing temperature in the preparation process of the prepreg, improves the mechanical property and the wet heat resistance, and does not reduce the dielectric property.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of hyperbranched polyester containing phosphorus terminal carboxyl groups is characterized in that the hyperbranched polyester is prepared by esterification polymerization of tricarboxyethyl phosphine and dihydric alcohol; the method comprises the following steps:
reacting tricarboxyethyl phosphine, dihydric alcohol and a catalyst in a solvent to obtain hyperbranched polyester containing phosphorus end carboxyl groups, wherein the catalyst is one or more selected from tetrabutyl titanate, p-toluenesulfonic acid, zinc acetate, sulfuric acid, phosphoric acid and tetrapropyl titanate, and the dosage of the catalyst is 0.3-1wt% of the total amount of the tricarboxyethyl phosphine and the dihydric alcohol; the reaction is carried out in a protective atmosphere, the temperature of the reaction is 100-200 ℃, and the reaction time is 1-10 h;
the mol ratio of the tricarboxyethyl phosphine to the dihydric alcohol is (n+1): n, wherein n is more than or equal to 3.
2. A phosphorus-containing hyperbranched epoxy resin, which is prepared by reacting phosphorus-containing carboxyl-terminated hyperbranched polyester prepared by the preparation method of claim 1 with epichlorohydrin.
3. Use of the phosphorus-containing hyperbranched epoxy resin according to claim 2 in resin compositions and/or fiber reinforcement.
4. An epoxy prepreg characterized in that it comprises a fiber reinforcement and the phosphorous hyperbranched epoxy resin according to claim 2.
5. The epoxy prepreg of claim 4, wherein the epoxy prepreg is composed of an epoxy resin, a fiber reinforcement material, and the phosphorus-containing hyperbranched epoxy resin of claim 2, wherein the phosphorus-containing hyperbranched epoxy resin is 5% -10% by weight of the epoxy resin, and the phosphorus-containing hyperbranched epoxy resin is 30% -70% by weight of the fiber reinforcement material.
6. The modified cyanate resin comprises, by mass, 100 parts of bisphenol type cyanate, 3-10 parts of toughening resin, 2-10 parts of epoxy resin, 0.5-10 parts of phosphorus-containing hyperbranched epoxy resin, 3-10 parts of flame retardant and 0.5-2 parts of coupling agent; the phosphorus-containing hyperbranched epoxy resin is the phosphorus-containing hyperbranched epoxy resin according to claim 2.
7. A cyanate ester prepreg consisting of the modified cyanate ester resin of claim 6 and a fiber reinforcement.
8. The cyanate ester prepreg according to claim 7, wherein the modified cyanate ester resin is 30-50 wt% of the cyanate ester prepreg.
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| CN101307139A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | Method for synthesizing phosphorus-containing polyester for fire retardant electronic packaging material |
| CN101475685A (en) * | 2009-01-15 | 2009-07-08 | 苏州海博特树脂科技有限公司 | Preparation method of hyperbranched polymer and hyperbranched epoxy resin |
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| CN107739433A (en) * | 2017-09-21 | 2018-02-27 | 四川大学 | 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 |
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| US20060258824A1 (en) * | 2003-04-17 | 2006-11-16 | Maki Oshima | Flame-retardant epoxy resin composition, prepregs containing the same, laminated sheets and printed wiring boards |
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| CN101307139A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | Method for synthesizing phosphorus-containing polyester for fire retardant electronic packaging material |
| CN101475685A (en) * | 2009-01-15 | 2009-07-08 | 苏州海博特树脂科技有限公司 | Preparation method of hyperbranched polymer and hyperbranched epoxy resin |
| CN105254866A (en) * | 2015-11-13 | 2016-01-20 | 四川大学 | Carboxyl-terminated phosphorus-containing copolyester, preparation method, halogen-free flame retardant biology-based pressure sensitive adhesive composed of carboxyl-terminated phosphorus-containing copolyester and application |
| CN107739433A (en) * | 2017-09-21 | 2018-02-27 | 四川大学 | 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 |
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