CN104403092A - Polyester curing agent with hyperbranched structure and synthetic method of polyester curing agent - Google Patents
Polyester curing agent with hyperbranched structure and synthetic method of polyester curing agent Download PDFInfo
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- CN104403092A CN104403092A CN201410773131.3A CN201410773131A CN104403092A CN 104403092 A CN104403092 A CN 104403092A CN 201410773131 A CN201410773131 A CN 201410773131A CN 104403092 A CN104403092 A CN 104403092A
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- solidifying agent
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- dissaving structure
- curing agent
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Abstract
The invention relates to a synthetic method of a polyester curing agent with a hyperbranched structure. The polyester curing agent is prepared from the following constituents in parts by weight: 230-240 parts of neopentyl glycol, 50-60 parts of trimethylolpropane, 160-180 parts of adipic acid, 150-190 parts of m-phthalic acid, 0.5-0.6 part of monobutyltin oxide, and 240-260 parts of terminated trimellitic anhydride. The synthetic method of the polyester curing agent provided by the invention is simple in synthetic process, easy in control of conditions, stable in production; the polyester curing agent is free of halogen and favorable to environment protection, so as to realize non-halogenation of an electronic packaging material; meanwhile, the selected raw materials are low in prices, so that the polyester curing agent used for curing epoxy resin can reduce the cost of epoxy resin.
Description
Technical field
The invention belongs to electronic package material field, especially a kind of polyester solidifying agent and synthetic method with dissaving structure.
Background technology
Epoxy resin is one of most widely used matrix resin in polymer matrix composite, polycondensation is carried out and obtained product by having the compound of epoxy group(ing) and multi-hydroxy or polyol compound, there is 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 the advantage such as with low cost, is widely used in the encapsulation of the electronic devices and components such as voltage dependent resistor, ceramic condenser, diode, triode.
But because the toughness of pure epoxy resin is not enough, cause curing material easily to become fragile, crack and cannot be used for the encapsulation that temperature cycle requires higher electronic devices and components, therefore, its application receives larger restriction.Based on this, Chinese scholars has carried out a large amount of study on the modification work to epoxy resin, summarizes many epoxy resin toughened methods: as adopted, expanded polystyrene veneer is epoxy resin toughened, liquid crystalline polymers is epoxy resin toughened, core-shell Polymer toughening epoxy resin, nano-particle toughening epoxy resin, macromole solidifying agent are epoxy resin toughened etc.
Although method for toughening is a lot, the actual method that can be applied to electronic package material, copper-clad plate base material and reinforcing bar protective system is also few.Because toughening material is used for electronic package material, copper-clad plate base material and reinforcing bar protective system must meet following five aspects: (1) toughening material is used for electronic package material, excellent stability in storage must be possessed; (2) toughening material is used for electronic package material, must ensure that electronic package material possesses excellent electrical property; (3) toughening material and epoxy resin have good consistency and can fully disperse in the epoxy; (4) toughening material is easy to process, makes modification be easy to carry out; Toughening material and epoxy resin mixing cured after, must ensure that electronic package material, copper-clad plate base material and reinforcing bar protective system possess excellent process based prediction model, as glass transition temperature Tg, thermotolerance, solvent-resisting should deteriorations.Therefore, the direct modified epoxy of macromole solidifying agent is adopted day by day to come into one's own; Wherein, the polymkeric substance of dissaving structure is owing to having low viscosity, high functionality, without the characteristic such as chain entanglement and good solubility, becoming a kind of epoxy resin toughened new way.
The present invention prepares a kind of multi-functional monomer synthesize polyester solidifying agent, thus makes polyester solidifying agent have dissaving structure, and after access, the epoxy resin of synthesis has better snappiness.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, a kind of the high-flexibility flame retardant polyester solidifying agent that snappiness is good, product with stable quality, resin color and luster are more shallow and the synthetic method with dissaving structure are provided.
The technical scheme that the present invention realizes object is as follows:
Have a polyester solidifying agent for dissaving structure, described component and parts by weight are stated as follows:
And described component and parts by weight are stated as follows:
Neopentyl glycol 230
TriMethylolPropane(TMP) 59
Hexanodioic acid 161
M-phthalic acid 183
Mono-n-butyltin 0.5
Trimellitic acid 1,2-anhydride 254.
And, described in there is the acid value 130-200mgKOH/g of the polyester solidifying agent of dissaving structure, melt viscosity is 1500 ~ 4000mPas/180 DEG C, and softening temperature is 80 ~ 120 DEG C.
Have a synthetic method for the polyester solidifying agent of dissaving structure, step is as follows:
(1) add neopentyl glycol and the TriMethylolPropane(TMP) that dissaving structure can be provided in a reservoir, heat up and stir, alcohol is melted;
(2) in the alcohol of fusing, add hexanodioic acid, m-phthalic acid and Mono-n-butyltin respectively, under logical nitrogen, be warming up to 150 DEG C, start esterification and produce esterification water to distillate;
(3) then carry out sectional type esterification, 150 ~ 180 DEG C of reacting by heating 2 ~ 4h, 180 ~ 220 DEG C of reacting by heating 1 ~ 3h, when esterification yield reaches more than 95%, vacuumize and carry out polycondensation, vacuum tightness-0.05 ~ 0MPa, the time 5 ~ 15min vacuumized;
(4) after polycondensation terminates, add trimellitic acid 1,2-anhydride end-blocking, stir, react 1 ~ 2h between 175 ~ 185 DEG C after, vacuumize, vacuum tightness-0.05 ~ 0MPa, time 5 ~ 10min;
(5) cooling discharge, through cooling compressing tablet, can obtain the polyester solidifying agent with dissaving structure.
Advantage of the present invention and positively effect are:
Simple, the condition of polyester solidifying agent synthesis technique provided by the invention be easy to control, administration measure, not halogen-containing, be conducive to environmental protection, can realize the non-halogen of electronic package material, meanwhile, the selected prices of raw and semifnished materials are cheap, therefore for epoxy resin cure, the cost of epoxy resin can be reduced.
(2) polyester solidifying agent provided by the invention has dissaving structure, has excellent snappiness and multi-functional, for the solidification of epoxy resin, not only can improve the snappiness of epoxy resin but also can improve the cross-linking density of epoxy resin.
(3) polyester solidifying agent provided by the invention has low viscosity, high functionality, without the characteristic such as chain entanglement and good solubility, makes the workability of electronic package material, physicals and electrical property etc. reach optimized degree.
(4) the present invention adopts sectional type synthesis technique, a kind of synthesis with the polyester solidifying agent of dissaving structure is achieved by adjusting the conditions such as each component proportion, temperature of reaction, reaction times, synthesized pet copolyester solidifying agent is used for epoxy electronic package material, snappiness is good, cross-linking density is large, intensity is large and achieve the non-halogen of electronic package material, optimize the workability of electronic package material, physicals and electrical property, give the snappiness of electronic package material excellence thus increase substantially the cold-hot impact of electronic package material.
Embodiment
Below by specific embodiment, the invention will be further described, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
The synthetic method of the polyester solidifying agent of dissaving structure of the present invention provides 2 embodiments altogether, and the finished product of synthesized polyester solidifying agent marks A, B respectively.
Embodiment 1
Have a synthetic method for the polyester solidifying agent (A) of dissaving structure, step is as follows:
Component is as follows: 230g neopentyl glycol, 59g TriMethylolPropane(TMP), 161g hexanodioic acid, 183g m-phthalic acid, 0.5g Mono-n-butyltin, 254g trimellitic acid 1,2-anhydride
Synthesis step is as follows:
(1) in the 1L four-hole boiling flask that heating jacket, agitator, thermometer, distillation column and prolong are housed, add 230g neopentyl glycol, 59g TriMethylolPropane(TMP), be heated to about 120 DEG C and stir fusing;
(2) add 161g hexanodioic acid, 183g m-phthalic acid and 0.4g Mono-n-butyltin again, logical nitrogen protection, after it dissolves, be slowly warming up to 150 DEG C and start esterification, and have water byproduct to flow out, control distillation column temperature in reaction process not higher than 100 DEG C,
(3) carry out sectional type esterification, 150 ~ 180 DEG C of reacting by heating 2 ~ 4h, 180 ~ 220 DEG C of reacting by heating 1 ~ 3h, when esterification yield reaches more than 95%, vacuumize and carry out polycondensation, vacuum tightness-0.05 ~ 0MPa, the time 5 ~ 15min vacuumized; .
(4) add 254g trimellitic acid 1,2-anhydride, react 2h at 175 ~ 185 DEG C after, vacuumize, vacuum tightness-0.05 ~ 0MPa, time 5 ~ 10min;
(5) discharging, through cooling compressing tablet, can obtain the polyester solidifying agent of light yellow clear shape dissaving structure.
The acid number of polyester solidifying agent A prepared by the present embodiment is 185mgKOH/g, and melt viscosity is 2250mPas/150 DEG C, and softening temperature is 109 DEG C.
Embodiment 2:
Have a synthetic method for the polyester solidifying agent (B) of dissaving structure, step is as follows:
Component is as follows: 230g neopentyl glycol, 56g TriMethylolPropane(TMP), 175g hexanodioic acid, 150g m-phthalic acid, 0.6g Mono-n-butyltin, 243g trimellitic acid 1,2-anhydride end-blocking.
Step is as follows:
(1) in the 1L four-hole boiling flask that heating jacket, agitator, thermometer, distillation column and prolong are housed, add 230g neopentyl glycol, 56g TriMethylolPropane(TMP), after being heated to about 120 DEG C stirring fusings;
(2) add 175g hexanodioic acid, 150g m-phthalic acid and 0.6g Mono-n-butyltin, logical nitrogen protection, after it dissolves, be slowly warming up to 150 DEG C and start esterification, and have water byproduct to flow out, control distillation column temperature in reaction process not higher than 100 DEG C,
(3) carry out sectional type esterification, 150 ~ 180 DEG C of reacting by heating 2 ~ 4h, 180 ~ 220 DEG C of reacting by heating 1 ~ 3h, when esterification yield reaches more than 95%, vacuumize and carry out polycondensation, vacuum tightness-0.05 ~ 0MPa, the time 5 ~ 15min vacuumized;
(4) add 243g trimellitic acid 1,2-anhydride, react 2h at 175 ~ 185 DEG C after, vacuumize, vacuum tightness-0.05 ~ 0MPa, time 5 ~ 10min;
(5) discharging, through cooling compressing tablet, can obtain the polyester solidifying agent of light yellow clear shape dissaving structure.
The acid number of polyester solidifying agent B prepared by the present embodiment is 178mgKOH/g, and melt viscosity is 1800mPas/150 DEG C, and softening temperature is 95 DEG C.
The each component mentioned in above-mentioned two embodiments also comprises following composition, and same function or effect the following stated component all can be adopted to substitute, and the solidifying agent obtained has equivalent effect, combines citing no longer one by one.
Acid value 130 ~ the 200mgKOH/g of the polyester solidifying agent of described dissaving structure, melt viscosity scope 1500 ~ 4000mPas/150 DEG C, softening point range 80 ~ 120 DEG C.
Testing performance index method involved in the present invention is as follows:
(1) the mensuration of acid number: according to GB6743-86 " assay method of paint and varnish paint base acid number " described mensuration;
(2) melt viscosity: use Brookfield cone-and-plate viscometer to measure the melt viscosity of phosphorous-containing polyester solidifying agent at different temperature;
(3) softening temperature: measure according to the method described in GB12007.6-89 " epoxy resin softening point measurement method ring and ball method ";
(4) cold-hot impact: be that the destructive test that ftractures is occurred in the environment of high temperature and low temperature successively alternation to the coating of electronic devices and components; The design temperature of high temperature and time length all can require to set according to difference, and low temperature is also like this; The resistance to high temperature of coating and a low temperature, be called a circulation; The cycle index of coating before cracking is more, and its cold-hot impact property is better.
Cold-hot impact condition involved in the present invention: high temperature is set as+125 DEG C, and low temperature is set as-40 DEG C, and a high temperature and a low temperature continuous time are 30min, voltage dependent resistor magnetic sheet used, diameter 20 Φ, often organizes experiment 10 prints.
Proof test: following three proof tests, the excellent results of the snappiness polyester solidifying agent of the dissaving structure prepared for the present invention.
The cold-hot impact of table 1 epoxy composite component proportion and coating curing thing
| Component | Unit | Reference example | Embodiment 1 | Embodiment 2 |
| Epoxy resin (E-12) | g | 50 | 35 | 35 |
| Solidifying agent: trimellitic acid 1,2-anhydride | g | 3.9 | — | — |
| There is the polyester solidifying agent A of dissaving structure | g | — | 15 | — |
| There is the polyester solidifying agent B of dissaving structure | g | — | — | 15 |
| Curing catalyst; Triphenyl phosphorus | g | 0.09 | 0.1 | 0.1 |
| Mineral filler: silicon-dioxide | g | 50 | 50 | 50 |
| Cold-hot impact | Individual | 20 | 90 | 80 |
Claims (4)
1. there is a polyester solidifying agent for dissaving structure, it is characterized in that: described component and parts by weight are stated as follows:
2. the polyester solidifying agent with dissaving structure according to claim 1, is characterized in that: described component and parts by weight are stated as follows:
Neopentyl glycol 230
TriMethylolPropane(TMP) 59
Hexanodioic acid 161
M-phthalic acid 183
Mono-n-butyltin 0.5
Trimellitic acid 1,2-anhydride 254.
3. the polyester solidifying agent with dissaving structure according to claim 1, it is characterized in that: described in there is the acid value 130-200mgKOH/g of the polyester solidifying agent of dissaving structure, melt viscosity is 1500 ~ 4000mPas/180 DEG C, and softening temperature is 80 ~ 120 DEG C.
4. there is a synthetic method for the polyester solidifying agent of dissaving structure as claimed in claim 1, it is characterized in that: step is as follows:
(1) add neopentyl glycol and the TriMethylolPropane(TMP) that dissaving structure can be provided in a reservoir, heat up and stir, alcohol is melted;
(2) in the alcohol of fusing, add hexanodioic acid, m-phthalic acid and Mono-n-butyltin respectively, under logical nitrogen, be warming up to 150 DEG C, start esterification and produce esterification water to distillate;
(3) then carry out sectional type esterification, 150 ~ 180 DEG C of reacting by heating 2 ~ 4h, 180 ~ 220 DEG C of reacting by heating 1 ~ 3h, when esterification yield reaches more than 95%, vacuumize and carry out polycondensation, vacuum tightness-0.05 ~ 0MPa, the time 5 ~ 15min vacuumized;
(4) after polycondensation terminates, add trimellitic acid 1,2-anhydride end-blocking, stir, react 1 ~ 2h between 175 ~ 185 DEG C after, vacuumize, vacuum tightness-0.05 ~ 0MPa, time 5 ~ 10min;
(5) cooling discharge, through cooling compressing tablet, can obtain the polyester solidifying agent with dissaving structure.
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| CN109348697A (en) * | 2018-11-17 | 2019-02-15 | 上海亿尚金属有限公司 | A kind of production technology of use for electronic products shielding case |
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| CN109348697A (en) * | 2018-11-17 | 2019-02-15 | 上海亿尚金属有限公司 | A kind of production technology of use for electronic products shielding case |
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Application publication date: 20150311 |