CN101307139A - Method for synthesizing phosphorus-containing polyester for fire retardant electronic packaging material - Google Patents
Method for synthesizing phosphorus-containing polyester for fire retardant electronic packaging material Download PDFInfo
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Abstract
The invention relates to a method for synthesizing phosphorous polyester used for fire-retardant electronic packaging materials, aiming to obtain the polyester with high fire resistance to solve the fire-retardant problem of the electronic packaging materials. The method for synthesizing the phosphorous polyester comprises the following steps that: firstly, polylol is added into a four-mouth flask, and the temperature is increased to over 100 DEG C so that the polylol is stirred to be melt; secondly, polyatomic acid/ estolide, reactive phosphorous compound and catalyst are respectively added into the molten polylol; the esterification reaction begins and esterifying water is generated and distilled off; thirdly, vacuum-pumping is performed for polycondensation when the esterification rate reaches over 95 percent; fourthly, end capping reagent is added and then the finished phosphorous polyester can be prepared, wherein, the acid value range is between 50 and 250 KOH/g, and the fusing temperature range is between 60 and 130 DEG C. The phosphorous polyester prepared by the method is used for the fire-retardant electronic packaging materials and can realize non-halogenation of the electronic packaging materials.
Description
Technical field
The invention belongs to the electronic package material field, especially a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material.
Background technology
Resins, epoxy is one of most widely used matrix resin in the polymer matrix composite, have excellent cohesiveness, chemical resistance, electrical insulation properties, mechanical property, and be easy to processing, shrinking percentage is low, coefficient of linear expansion is little and advantage such as with low cost, is widely used in the encapsulation of electronic devices and components such as voltage dependent resistor, ceramic condenser, diode, triode.Because the limiting oxygen index(LOI) (LOI) of Resins, epoxy is lower, has only 19.5, belongs to combustible material, therefore need carry out fire-retardant finish to it.Usually, the method for improving ethoxyline resin antiflaming is to introduce halogen-containing fire retardant in Resins, epoxy, and cooperates the flame retardant as the antimonous oxide class, thereby gives Resins, epoxy with flame retardancy and self-extinguishing.But nowadays, the flame retardant of antimonous oxide class has been listed in carcinogenic substance, and halogen flame can produce dioxin toxic smoke and corrosive gasess such as (Dioxin) when burning, has had a strong impact on human beings'health and human environment of depending on for existence.For human health and requirement on environmental protection, developing halogen-free flame retardants harmless, free from environmental pollution and that flame retarding efficiency is high has become the research focus.
In halogen-free flame retardants, the fire retardant that phosphorus series compound has the environmental protection notion as a new generation is by extensive studies and application.And in phosphorus flame retardant, can satisfy environmental requirement and the fire retardant that has than high flame retardant mainly is an organic phosphorus flame retardant.Press fire retardant and by the relation between the flame-retardant polymer, organic phosphorus flame retardant can be divided into additive flame retardant and reactive flame retardant usually.Chemical reaction does not take place in other components in additive flame retardant and polymkeric substance and the polymkeric substance, is scattered in the polymkeric substance in the mode of physical mixed, thereby gives the base material flame retardant resistance; Reactive flame retardant then participates in chemical reaction as the monomer of superpolymer or as cure-crosslinking agent, thereby gives because the polymkeric substance flame retardant resistance.Thereby the technology of addition type phosphorus flame retardant is simple, but flame retarding efficiency is low, addition is big, and has problems such as dispersiveness, consistency, thereby has limited the use of additive flame retardant.Characteristics such as reactive flame retardant then has efficiently, high flame retardant, non-fugacity, thermotolerance become the first-selection research of organic phosphorus flame retardant, also are the preferred approach that realizes ethoxyline resin antiflaming.
By the response type method phosphoric is introduced Resins, epoxy and can be divided into dual mode: the one, synthetic phosphorated Resins, epoxy, as No. 5376453, United States Patent (USP), promptly use the phosphoric acid ester of band oxygen base to cooperate nitrogenous solidifying agent to make veneer sheet, thereby make its flame retardant resistance reach the requirement of UL94V-0; The 2nd, synthetic phosphorated solidifying agent.Based on the characteristics and the prior art of electronic devices and components packaged material, the present invention turns to starting point with the halogen-free flameproof of electronic devices and components packaged material, proposes a kind of novel phosphorus-containing solidifying agent-phosphorous-containing polyester.
Synthetic method about phosphorous-containing polyester, disclose a kind of pre-esterifying liquid at CN101065417A and added the method for carrying out copolymerization in polyvalent alcohol and the polycarboxylic acid P contained compound and ethylene glycol, the necessary prepared beforehand phosphotidic liquid of this method can not be realized continuity production.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material is provided, institute's synthetic phosphorous-containing polyester technology is simple, produces stable; More particularly, the present invention relates to the carboxyl flame retardant polyester of a kind of acid number at 50～250mgKOH/g, phosphorus content 1～10wt%, this flame retardant polyester is used for electronic package material, and its consumption just can realize that at 5～20wt% the flame retardant resistance of electronic package material reaches the standard of UL94V0 level.
The present invention realizes that the technical scheme of its purpose is:
A kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material, its synthetic method comprises the steps:
(1). in the four-hole boiling flask that heating jacket, agitator, thermometer, distillation column and prolong are housed, add polyvalent alcohol, be warming up to and make polyvalent alcohol stirring fusing more than 100 ℃;
(2). in molten polyol, add polyprotonic acid/acid anhydrides, response type P contained compound and catalyzer respectively, be warming up to 170～190 ℃ under the logical nitrogen and begin esterifications and produce esterification water to distillate;
(3). slowly be warming up to 240～270 ℃,, vacuumize and carry out polycondensation, vacuum tightness-0.07～0MPa, the time 20～30min that vacuumizes when esterification yield reaches 95% when above;
(4). after polycondensation finishes, add end-capping reagent, stir, after reacting 1～2h between 170～190 ℃, vacuumize, vacuum tightness-0.06～0MPa, time 10～20min can prepare the phosphorous-containing polyester finished product; The acid number of this phosphorous-containing polyester finished product is 50～250mgKOH/g, and melt viscosity is 500～8000mPas/180 ℃, and softening temperature is 60～130 ℃, and phosphorus content is 1～10wt%.
And the weight percent of the polyvalent alcohol that is added, polyprotonic acid/acid anhydrides, response type P contained compound and catalyzer is respectively: polyvalent alcohol 10～30%; Polyprotonic acid/acid anhydrides 0～25%; Response type P contained compound 10～75%; Catalyzer 0.02～0.1%; End-capping reagent 5～40%.
And described esterification is the sectional type esterification, i.e. 180～220 ℃ of reacting by heating 5h, 220～240 ℃ of reacting by heating 4h, 240～270 ℃ of reacting by heating 3～4h when the acid number of reaction system during less than 18mgKOH/g, vacuumize polycondensation.
And, vacuumizing when carrying out polycondensation, vacuum tightness is-0.07～0MPa, the time that vacuumizes is 20～30min; Polycondensation when acid number is between 2～5mgKOH/g, is cooled to 200 ℃ and promptly adds end-capping reagent after finishing.
And described polyvalent alcohol is that ethylene glycol, Diethylene Glycol, propylene glycol, 2-methyl 1,3 propylene glycol, glycerol, TriMethylolPropane(TMP), neopentyl glycol are wherein at least a.
And described polyprotonic acid/acid anhydrides is the wherein at least a of terephthalic acid, m-phthalic acid, pentanedioic acid, hexanodioic acid, dimeracid, trimellitic acid 1,2-anhydride.
And, described response type P contained compound, refer to contain in its molecular structure can with polyvalent alcohol or polyprotonic acid reactive activity group, as 2-carboxyethyl phenyl phosphinic acid (CEPPA), hydroxymethyl phenyl phospho acid (HMPPA), three (3-hydroxypropyl) phosphine oxide, two (to carboxyphenyl) phenyl phosphine oxide (BCPPO), [(6-oxygen-(6H)-dibenzo-(c, e) methyl oneself ring-6-ketone of (1,2)-oxygen phospha)]-Succinic Acid (DDP), ODOPB, DOPOMA wherein at least a.
And described catalyzer is the wherein a kind of of tetrabutyl titanate, titanium isopropylate, metatitanic acid four different monooctyl esters, butyl stannic oxide, Dibutyltin oxide.
And described end-capping reagent is Tetra hydro Phthalic anhydride, isophthalic anhydride or trimellitic acid 1,2-anhydride.
The present invention has the following advantages:
(1). phosphorous-containing polyester synthesis technique provided by the invention is simple, condition is easy to control, it is stable to produce.
(2). phosphorous-containing polyester provided by the invention is not halogen-containing, helps environmental protection.
(3). phosphorous-containing polyester provided by the invention is used for electronic package material, can realize the non-halogen of electronic package material.
(4). the present invention directly carries out pre-mixing with P contained compound and polyvalent alcohol, polycarboxylic acid, adopt sectional type esterification and polycondensation, realized the synthetic of a kind of phosphorous-containing polyester that can be used for fire retardant electronic packaging material by conditions such as control reaction temperature, reaction times, synthesize to such an extent that phosphorous-containing polyester is used for electronic package material, phosphoric does not move, the flame retarding efficiency height; And synthetic method craft is simple, produces stable.
Embodiment
The invention will be further described below in conjunction with specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Testing performance index method involved in the present invention is as follows:
(1). the mensuration of acid number: according to the described mensuration of GB6743-86 " the paint and varnish assay method of the basic acid number of lacquer ";
(2). the mensuration of phosphorus content: measure according to the method described in the people such as Hu Hanfang, Ma Zhiling " mensuration of Phosphorus Content in Phosphorated Flame Retardant ";
(3). melt viscosity: use the Brookfield cone-and-plate viscometer under different temperature, to measure the melt viscosity of phosphorous-containing polyester solidifying agent;
(4). softening temperature: measure according to the method described in the GB12007.6-89 " Resins, epoxy softening point measurement method ring and ball method ";
(5). flame retardant resistance is measured: according to the testing vertical flammability method among the UL94 " the flammable performance test of equipment and device component material ", determine the flame retardant rating of matrix material.Batten size: long 125 ± 5mm, wide 13.0 ± 0.5mm, thickness 1.5 ± 0.2mm;
The synthetic method of phosphorous-containing polyester provides 3 embodiment altogether among the present invention.
Embodiment 1:
Heating jacket is being housed, agitator, thermometer, in the 1L four-hole boiling flask of distillation column and prolong, add 12.07g ethylene glycol, 8.76g2-methyl 1,3 propylene glycol, 233.26g neopentyl glycol, after the heated and stirred fusing, add the 5.69g hexanodioic acid, the 110g terephthalic acid, 6.47g m-phthalic acid, 133.45gCEPPA, 202.28gDDP and 0.6g tetrabutyl titanate, after treating its dissolving, be warming up to 180 ℃ of beginning esterifications and produce esterification water and distillate, control distillation column temperature is not higher than 100 ℃ in the reaction process, carry out the sectional type esterification then, 180～220 ℃ of reacting by heating 5h, 220～240 ℃ of reacting by heating 4h, 240～270 ℃ of reacting by heating 3～5h, when the acid number of reaction system during less than 18mgKOH/g, vacuumize polycondensation, vacuum tightness is-0.05MPa that the time that vacuumizes is 30min; When acid number is between 2～5mgKOH/g, be cooled to 200 ℃, add 224.47g trimellitic acid 1,2-anhydride end-blocking, behind reaction 1.5h under 170～190 ℃, vacuumize, vacuum tightness is-0.04MPa, the time that vacuumizes is 15min, and discharging then promptly gets the phosphorous-containing polyester finished product.
The acid number of gained phosphorous-containing polyester is 152.3mgKOH/g, and softening temperature is 110 ℃, and 180 ℃ are surveyed its melt viscosity is 2200mPas, and phosphorus content is 4.29wt%.Phosphorous-containing polyester and bisphenol A type epoxy resin and other components are carried out melting mixing extrude, making amount of polyester at last is that 10wt%, phosphorus content are the epoxy electronic package material of 0.44wt%.Flame retardant resistance: UL94V0 level, 5 batten total combustion time of 30s.
Embodiment 2:
Heating jacket is being housed, agitator, thermometer, in the 1L four-hole boiling flask of distillation column and prolong, add 10.54g ethylene glycol, 9.56g2-methyl 1,3 propylene glycol, 254.46g neopentyl glycol, after the heated and stirred fusing, add the 6.21g hexanodioic acid, the 120g terephthalic acid, 7.06g m-phthalic acid, 236.58gCEPPA, 73.56gDDP and 0.6g tetrabutyl titanate, after treating its dissolving, be warming up to 180 ℃ of beginning esterifications and produce esterification water and distillate, control distillation column temperature is not higher than 100 ℃ in the reaction process, carry out the sectional type esterification then, 180～220 ℃ of reacting by heating 5h, 220～240 ℃ of reacting by heating 4h, 240～270 ℃ of reacting by heating 3～5h, when the acid number of reaction system during less than 18mgKOH/g, vacuumize polycondensation, vacuum tightness-0.05MPa, the time that vacuumizes is 30min; When acid number is between 2～5mgKOH/g, be cooled to 200 ℃, add 228.56g trimellitic acid 1,2-anhydride end-blocking, behind reaction 1.5h under 170～190 ℃, vacuumize, vacuum tightness is-0.04MPa, the time that vacuumizes is 15min, and discharging then promptly gets the phosphorous-containing polyester finished product.
The acid number of gained phosphorous-containing polyester is 153mgKOH/g, and softening temperature is 106 ℃, and 180 ℃ are surveyed its melt viscosity is 1980mPas, and phosphorus content is 4.68wt%.Making amount of polyester at last is that 10wt%, phosphorus content are the epoxy electronic package material of 0.48wt%.Flame retardant resistance: UL94V0 level, 5 batten total combustion time of 24s.
Embodiment 3:
Heating jacket is being housed, agitator, thermometer, in the 1L four-hole boiling flask of distillation column and prolong, add 8.23g ethylene glycol, 9.96g2-methyl 1,3 propylene glycol, 265.07g neopentyl glycol, after the heated and stirred fusing, add the 6.47g hexanodioic acid, the 125g terephthalic acid, 7.35g m-phthalic acid, 293.82gCEPPA and 0.6g tetrabutyl titanate, after treating its dissolving, be warming up to 180 ℃ of beginning esterifications and produce esterification water and distillate, control distillation column temperature is not higher than 100 ℃ in the reaction process, carry out the sectional type esterification then, 180～220 ℃ of reacting by heating 5h, 220～240 ℃ of reacting by heating 4h, 240～270 ℃ of reacting by heating 3～5h, when the acid number of reaction system during less than 18mgKOH/g, vacuumize polycondensation, vacuum tightness is-0.05MPa that the time that vacuumizes is 30min; When acid number is between 2～5mgKOH/g, be cooled to 200 ℃, add 221.07g trimellitic acid 1,2-anhydride end-blocking, behind reaction 1.5h under 170～190 ℃, vacuumize, vacuum tightness is-0.04MPa, the time that vacuumizes is 15min, and discharging then promptly gets the phosphorous-containing polyester finished product.
The acid number of gained phosphorous-containing polyester is 150mgKOH/g, and softening temperature is 100 ℃, and 180 ℃ are surveyed its melt viscosity is 1800mPas, and phosphorus content is 4.95wt%.Making amount of polyester at last is that 10wt%, phosphorus content are the epoxy electronic package material of 0.68wt%.Flame retardant resistance: UL94V0 level, 5 batten total combustion time of 15s.
Claims (9)
1. synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material, it is characterized in that: synthetic method comprises the steps:
(1). in the four-hole boiling flask that heating jacket, agitator, thermometer, distillation column and prolong are housed, add polyvalent alcohol, be warming up to and make polyvalent alcohol stirring fusing more than 100 ℃;
(2). in molten polyol, add polyprotonic acid/acid anhydrides, response type P contained compound and catalyzer respectively, be warming up to 170～190 ℃ under the logical nitrogen and begin esterifications and produce esterification water to distillate;
(3). slowly be warming up to 240～270 ℃,, vacuumize and carry out polycondensation, vacuum tightness-0.07～0MPa, the time 20～30min that vacuumizes when esterification yield reaches 95% when above;
(4). after polycondensation finishes, add end-capping reagent, stir, after reacting 1～2h between 170～190 ℃, vacuumize, vacuum tightness-0.06～0MPa, time 10～20min can prepare the phosphorous-containing polyester finished product; The acid number of this phosphorous-containing polyester finished product is 50～250mgKOH/g, and melt viscosity is 500～8000mPas/180 ℃, and softening temperature is 60～130 ℃, and phosphorus content is 1～10wt%.
2. a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material according to claim 1, it is characterized in that: the weight percent of the polyvalent alcohol that is added, polyprotonic acid/acid anhydrides, response type P contained compound and catalyzer is respectively: polyvalent alcohol 10～30%; Polyprotonic acid/acid anhydrides 0～25%; Response type P contained compound 10～75%; Catalyzer 0.02～0.1%; End-capping reagent 5～40%.
3. a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material according to claim 1, it is characterized in that: described esterification is the sectional type esterification, i.e. 180～220 ℃ of reacting by heating 5h, 220～240 ℃ of reacting by heating 4h, 240～270 ℃ of reacting by heating 3～4h, when the acid number of reaction system during, vacuumize polycondensation less than 18mgKOH/g.
4. a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material according to claim 1 is characterized in that: vacuumizing when carrying out polycondensation, vacuum tightness is-0.07～0MPa, and the time that vacuumizes is 20～30min; Polycondensation when acid number is between 2～5mgKOH/g, is cooled to 200 ℃ and promptly adds end-capping reagent after finishing.
5. a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material according to claim 1 and 2, it is characterized in that: described polyvalent alcohol is that ethylene glycol, Diethylene Glycol, propylene glycol, 2-methyl 1,3 propylene glycol, glycerol, TriMethylolPropane(TMP), neopentyl glycol are wherein at least a.
6. a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material according to claim 1 and 2 is characterized in that: described polyprotonic acid/acid anhydrides is the wherein at least a of terephthalic acid, m-phthalic acid, pentanedioic acid, hexanodioic acid, dimeracid, trimellitic acid 1,2-anhydride.
7. a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material according to claim 1 and 2, it is characterized in that: described response type P contained compound, refer to contain in its molecular structure can with polyvalent alcohol or polyprotonic acid reactive activity group, as 2-carboxyethyl phenyl phosphinic acid (CEPPA), hydroxymethyl phenyl phospho acid (HMPPA), three (3-hydroxypropyl) phosphine oxide, two (to carboxyphenyl) phenyl phosphine oxide (BCPPO), [(6-oxygen-(6H)-dibenzo-(c, e) the methyl own ring-6-ketone of (1,2)-oxygen phospha)]-Succinic Acid (DDP), ODOPB, DOPOMA's is wherein at least a.
8. a kind of synthetic method that is used for the phosphorous-containing polyester of fire retardant electronic packaging material according to claim 1 and 2 is characterized in that: described catalyzer is the wherein a kind of of tetrabutyl titanate, titanium isopropylate, metatitanic acid four different monooctyl esters, butyl stannic oxide, Dibutyltin oxide.
9. according to claim 1 or 2 or 4 described a kind of synthetic methods that are used for the phosphorous-containing polyester of fire retardant electronic packaging material, it is characterized in that: described end-capping reagent is Tetra hydro Phthalic anhydride, isophthalic anhydride or trimellitic acid 1,2-anhydride.
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