CN104804185B - Preparation method of cyanate ester prepolymer used for preparing glue film - Google Patents
Preparation method of cyanate ester prepolymer used for preparing glue film Download PDFInfo
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- CN104804185B CN104804185B CN201510201306.8A CN201510201306A CN104804185B CN 104804185 B CN104804185 B CN 104804185B CN 201510201306 A CN201510201306 A CN 201510201306A CN 104804185 B CN104804185 B CN 104804185B
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- cyanate
- cyanate ester
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Abstract
The invention discloses a cyanate ester prepolymer used for preparing a glue film and a preparation method of the cyanate ester prepolymer, and relates to the technical field of polymer materials, in particular to a prepolymer composition and a preparation method thereof and aims to solve the technical problems of the existing method that the reaction temperature is high, the yield is low, and implosion easily occurs. The cyanate ester prepolymer for preparing the glue film is made of thermoplastic polysulfone resin and bisphenol A type cyanate ester prepolymer. The method for preparing cyanate ester prepolymer includes the following steps: thermoplastic polysulfone resin is added into liquid cyanate ester until thermoplastic polysulfone resin is totally dissolved; a polymerization catalyst is added for reacting; after the reaction is carried out for 2 hours, polymerization product is taken every 10 minutes and placed on a piece of isolation paper for 5 minutes; the polymerization reaction is ended when the product becomes transparent and can be stripped off from the isolation paper, and the cyanate ester prepolymer used for preparing the glue film is obtained. The invention further provides a method for preparing the cyanate ester prepolymer composition, and solves the problems of the existing process that the reaction temperature is high, the process is difficult to control, the yield is low, and implosion easily occurs.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of performed polymer compositionss and preparation method thereof.
Background technology
Cyanate ester resin has a structural and functional class high performance resin while being and develop the eighties in 20th century
Material, commercialization is realized the nineties, and hereafter its application has obtained fast development.
Cyanate ester monomer molecular formula
Compared with ripe high performance resin, the good process with epoxy resin strengthens span tree to cyanate ester resin
High-temperature behavior as lipid, the heatproof combustion resistance of phenolic resin.
The cyanate ester resin of table 1. and other high-performance thermosetting resin key propertys compare
| Performance | Epoxy | Phenolic aldehyde | Strengthen span | Cyanate |
| Density g/cm3 | 1.2~1.25 | 1.24~1.32 | 1.2~1.3 | 1.1~1.35 |
| Using temperature DEG C | 180 | 200~250 | 200 | 200 |
| Stretch moduluses GPa | 3.1~3.8 | 3~5 | 3.4~4.1 | 3.1~3.4 |
| DIELECTRIC CONSTANT ε 1MHz | 3.8~4.5 | 4.3~5.4 | 3.4~3.7 | 2.7~3.2 |
| Solidification temperature DEG C | 180 | 150~190 | 220~300 | 180~250 |
| TGA starting weightless temperatures DEG C | 260~340 | 300~360 | 360~400 | 400~420 |
Specifically：The dielectric properties of cyanate ester resin are that other resins are incomparable.Cyanate ester resin
After cured, reaction generates the triazine ring network structure of high degree of symmetry：
Cyanate solidfied material symmetrical structure
The structure of this high degree of symmetry causes whole molecule to form a resonance system, under electromagnetic field effect, shows
Extremely low dielectric loss (tan δ are 0.001~0.008) and low and stable dielectric constant；And when frequency changes,
This molecular structure is insensitive to dielectric relaxor etc., the characteristics of with usage frequency width (8~100GHz)；While cyanate ester resin
Dielectric properties within the scope of broad temperature (- 160 DEG C~200 DEG C), vary less.
In addition to thermostability is high, dielectric properties are excellent, the triazine ring structure of the high degree of symmetry of cyanate molecular skeleton is also
Determine that its product has agent of low hygroscopicity, dimensional stability, thermal coefficient of expansion low and isotropic advantage, therefore extensively use
Make electromagnetic wave transparent material, structural material, high temperature resistant adhesivess.In aerospace field, cyanate ester resin is mainly used in anti-destructive
Technique for aircraft composite, sandwich of layers, RTM techniques, radome, nose cone and antenna, the low property detected composite, telecommunication satellite
With other space applications；It is mainly used in microelectronic encapsulation, multilayer circuit board and multi-chip module in electronic applications.
According to product form, cyanate product is broadly divided into prepreg, RTM resins, pasty state glue, glued membrane, composite foam etc.
Five classes.Wherein glued membrane (including membranaceous adhesive and membranaceous foamed adhesive) is most important structure glue in aerospace industry application
Stick, with light weight, wave transmission rate is high, broadband properties are good the characteristics of.In honeycomb sandwich construction, the splicing of honeycomb core, filling,
Edge sealing, reinforcement and the fixation of various inserts mainly use membranaceous foamed adhesive；High-performance blister eyelid covering is tied with honeybee core
The bonding of structure mainly uses membranaceous adhesive.
Cyanate glued membrane be one kind based on cyanate performed polymer resin, add curing catalysts, polymerization inhibitor, filler,
The components such as thixotropic agent, toughener, foaming agent, the semisolid prepared through multiple techniques such as mixing, press mold simultaneously has certain
Flexible membranaceous adhesive.The component thing of most critical is cyanate performed polymer in cyanate glued membrane component, the structure of performed polymer,
The Determines processing performance of downstream product (including film property, wellability, trickling property, tack, stickup property, storage characteristics etc.)
And mechanical property, heat resistance, dielectric properties.
The B of CN 101402729 disclose a kind of cyanate resin composition and preparation method thereof.The method is double by tetramethyl
Phenol F types cyanate is polymerized at 190~220 DEG C, obtains tetramethyl bisphenol-f type cyanate performed polymer.Again by the performed polymer for obtaining
A kind of compositionss are mixed to get with the bisphenol E-type cyanate of liquid, this compositionss are at normal temperatures liquid, can apply to twine
Around or RTM moulding processs.
The B of CN 102199289 disclose a kind of preparation method of tetramethyl bisphenol F type cyanate resin prepolymer.In nitrogen
In atmosphere, by solid-state tetramethyl bisphenol F cyanate resin heating for dissolving；Polymerization accelerant is added, it is anti-at 150~170 DEG C
Should；Cool down when index of refraction is 1.5750~1.5650, obtain liquid reactant；Butanone is added, it is non-volatile in the product for obtaining
Thing content >=65.36%.
Cyanate performed polymer product involved by above patent is liquid, and the performed polymer used in cyanate glued membrane should
Cannot act as preparing the base of glued membrane for solvent-free flexible semisolid product, therefore the cyanate performed polymer involved by above patent
Plinth resin.
The B of patent CN 101935514 discloses a kind of foam structural adhesive and preparation method thereof, is directed to cyanate pre-
The preparation method of aggressiveness：Bisphenol A cyanate ester resin or bisphenol A cyanate ester resin are protected with polysulfone resin mixture in nitrogen
Under shield, heat and stir in 160~180 DEG C and reacted, it is sagging immediately up to the polymer that reaction generation is dipped with Glass rod
Stop heating when pulling into the strip of 15~20cm, discharge immediately, then cool down, obtain cyanate performed polymer.Using the technique
During production, prepolymerization reaction process is wayward, and reaction end is difficult to hold, satisfactory semisolid, flexible pre-
Aggressiveness yield rate is not high.Reason is：The polyreaction of cyanate ester monomer is that cyanate group (- OCN) is being heated and catalyst work
With the process of lower trimerization cyclization, pre-polymerization process control is actually during monomer cure the terminating reaction on certain point, thus
The intermediate product for obtaining is exactly the performed polymer it is desirable that obtaining.Calculated according to DSC, cyanate polymerization reaction heat △ H are about
400J/g, result is caused by thermal discharge is so high：In 160~180 DEG C of reaction intervals, the rapid heat release of curing reaction, enter one
Step raises internal temperature, and hardening phase is completed at short notice, or even moment " implode " phenomenon occurs, and decomposition discharges a large amount of
Toxic gas, it is impossible to obtain flexible intermediate product.
In sum, the cyanate performed polymer preparation work that the gentle steady, reaction end of course of reaction is easily controlled is developed
Skill has important practical significance.
The content of the invention
The invention aims to solve existing method reaction temperature height, process hardly possible is controlled, yield rate is low, easy generation
A kind of technical problem of " implode ", there is provided preparation method for preparing the cyanate performed polymer of glued membrane.
For prepare the cyanate performed polymer of glued membrane by thermoplasticity polysulfones resinoid and bisphenol A cyanate ester prepolymer according to
10~35:100 mass ratio is made.
The monomer of described bisphenol A cyanate ester prepolymer is white crystal, and fusing point is 80 DEG C, and molecular structure is：
Described thermoplasticity polysulfones resinoid be polysulfone resin, polyethersulfone resin or polyaryl ether sulphone resin,
Wherein polysulfone resin, its molecular formula is：
In formula：2
≤ n≤20,
Polyethersulfone resin, its molecular formula is：
In formula：2≤n≤20, polyarylether
Sulphone resin, its molecular formula is：
In formula：2≤n≤20.
The above-mentioned preparation method for preparing the cyanate performed polymer of glued membrane is as follows：
First, bisphenol A cyanate ester prepolymer is heated to being completely melt to become homogeneous liquid, obtains liquid cyanate；
2nd, under conditions of temperature is 110~120 DEG C, stirs, thermoplasticity polysulfones resinoid is added in liquid cyanate
Until thermoplasticity polysulfones resinoid is completely dissolved, polymerization catalyst is added, the addition of polymerization catalyst is liquid cyanate matter
1~the 5 ‰ of amount, carry out 2~6h of polyreaction at 120~130 DEG C；
3rd, after the polyreaction of step 2 carries out 2h, take 5-10 gram of polymerizate every 10min and place to release paper
5min, and is polyreaction terminal when can stripping down from release paper when observing that product is transparent, lowers the temperature, goes out
Material, obtains final product the cyanate performed polymer for preparing glued membrane.
In step one bisphenol A cyanate ester prepolymer is heated to being completely melt at 80 DEG C~120 DEG C.
Polymerization catalyzed described in step 2 for acetylacetone copper and the mixture of 4- nonyl phenols, wherein acetylacetone copper with
The mass ratio of 4- nonyl phenols is (1~5):100.
The solidification of cyanate ester monomer be cyanate group (- OCN) in the process with trimerization cyclization under catalyst action of being heated,
Pre-polymerization process control is actually during monomer cure the terminating reaction on certain point, thus obtained intermediate product, also
It is prepolymer.Calculated according to DSC, the hot △ H of curing reaction of bisphenol A cyanate ester are about 400J/g, and thermal discharge is so high to lead
The result of cause is：Once temperature is reached on initiation temperature, the rapid heat release of curing reaction, internal temperature is further raised, short
Hardening phase is completed in time, or even moment " implode " phenomenon occurs, it is impossible to obtain flexible cyanate performed polymer.
But there is the temperature spot of two keys in cyanate polymerization process：" pre-polymerization temperature flex point " and " implode temperature is turned
Point ".During less than " pre-polymerization temperature flex point ", reaction is slow or does not react；When temperature is increased to " implode temperature flex point ", reaction speed
Degree is rapid to be increased, and internal temperature is drastically raised, and moment " implode " phenomenon occurs, and decomposition discharges a large amount of toxic gas, reaction stream
Journey is as shown in Figure 1.Between the two temperature flex points, there is a narrow process window, this process window is exactly institute of the present invention
The polymeric reaction temperature stated is interval, i.e., between 120~130 DEG C, in this temperature range, polymeric reaction temperature is relatively low, reaction is gentle
Steadily, course of reaction is easily controlled.
Carry out between 120~130 DEG C in polymerization process, prolongation over time, conversion ratio is gradually stepped up, product
It is as shown in Figure 2 to there is following change in outward appearance.
Can be seen that under too low or mistake high conversion by figure 1 above and Fig. 2, polymerizate is hard material.Only
The terminating reaction when conversion ratio reaches particular value, can just obtain the performed polymer for being suitable for compression into film with pliability, ductility.
The present invention to be polymerized terminal determination through the following steps that realize：After polyreaction carries out 2h, every
10min takes a small amount of polymerizate to release paper, and room temperature places 5min, and when observing that product is transparent, feel is flexible and can be light
It is easy when stripping down from release paper, it is judged as polyreaction terminal, cooling, discharging.
The present invention for preparing the cyanate performed polymer of glued membrane without any solvent, be it is a kind of have pliability, ductility,
The semisolid product of tack, is the ideal original for preparing cyanate glued membrane (including membranaceous adhesive and membranaceous foamed adhesive)
Material.Present invention also offers the preparation method of the cyanate performed polymer compositionss, solves existing process reaction temperature height, mistake
Journey hardly possible is controlled, yield rate is low, easy generation " implode " difficult problem.
Description of the drawings
Fig. 1 is cyanate polymerization process reacting flow chart；
Fig. 2 is carried out between 120~130 DEG C in polymerization process, product appearance variation diagram.
Specific embodiment
Technical solution of the present invention is not limited to act specific embodiment set forth below, also including between each specific embodiment
Combination in any.
Specific embodiment one：Present embodiment is used to prepare the cyanate performed polymer of glued membrane by thermoplasticity polysulfones resinoid
With bisphenol A cyanate ester prepolymer according to 10~35:100 mass ratio is made.
Specific embodiment two：Present embodiment and bisphenol A cyanate ester described unlike specific embodiment one
The monomer molecule structure of prepolymer is：
Thermoplasticity polysulfones resinoid and bisphenol-A
The mass ratio of type cyanate prepolymer is 15~25:100.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment and thermoplasticity described unlike specific embodiment one or one of two
Polysulfones resinoid be polysulfone resin, polyethersulfone resin or polyaryl ether sulphone resin,
Wherein polysulfone resin, its molecular formula is：
In formula：2
≤ n≤20,
Polyethersulfone resin, its molecular formula is：
In formula：2≤n≤20,
Polyaryl ether sulphone resin, its molecular formula is：
In formula：2≤n≤20.Its
It is identical with specific embodiment one or one of two.
Specific embodiment four：The preparation side for preparing the cyanate performed polymer of glued membrane described in specific embodiment one
Method is as follows：
First, bisphenol A cyanate ester prepolymer is heated to being completely melt to become homogeneous liquid, obtains liquid cyanate；
2nd, under conditions of temperature is 110~120 DEG C, stirs, thermoplasticity polysulfones resinoid is added in liquid cyanate
Until thermoplasticity polysulfones resinoid is completely dissolved, polymerization catalyst is added, the addition of polymerization catalyst is liquid cyanate matter
1~the 5 ‰ of amount, carry out 2~6h of polyreaction at 120~130 DEG C；
3rd, after the polyreaction of step 2 carries out 2h, 5~10g polymerizates are taken every 10min and is placed to release paper
5min, and is polyreaction terminal when can stripping down from release paper when observing that product is transparent, lowers the temperature, goes out
Material, obtains final product the cyanate performed polymer for preparing glued membrane.
Specific embodiment five：Present embodiment from step one unlike specific embodiment four by bisphenol A-type cyanogen
Acid esters prepolymer is heated to being completely melt at 80 DEG C~120 DEG C.Other are identical with specific embodiment four.
Specific embodiment six：Present embodiment is poly- described in step 2 from unlike specific embodiment four or five
Close mixture of the catalysis for acetylacetone copper and 4- nonyl phenols, wherein the mass ratio of acetylacetone copper and 4- nonyl phenols for (1~
5):100.Other are identical with specific embodiment four or five.
The preparation method of polymerization catalyst：1Kg4- nonyl phenols are added in 2.5L stainless steel cauldrons, 100~120 are heated to
DEG C, 30g acetylacetone coppers are added under agitation, between 100~120 DEG C, after 2h, acetylacetone copper is complete for maintenance system temperature
In being dissolved in 4- nonyl phenols, now system is black-and-blue uniform solution.
Specific embodiment seven：In temperature in step 2 unlike one of present embodiment and specific embodiment four to six
Under conditions of spending for 115 DEG C, stirring, thermoplasticity polysulfones resinoid is added in liquid cyanate until thermoplasticity polysulfones resinoid
It is completely dissolved.Other are identical with one of specific embodiment four to six.
Specific embodiment eight：It is polymerized in step 2 unlike one of present embodiment and specific embodiment four to seven
The addition of catalyst is 2~the 4 ‰ of liquid cyanate quality.Other are identical with one of specific embodiment four to seven.
Specific embodiment nine：It is polymerized in step 2 unlike one of present embodiment and specific embodiment four to eight
The addition of catalyst is the 3 ‰ of liquid cyanate quality.Other are identical with one of specific embodiment four to eight.
Specific embodiment ten：In step 2 unlike one of present embodiment and specific embodiment four to nine
2~6h of polyreaction is carried out at 125 DEG C.Other are identical with one of specific embodiment four to nine.
Using following experimental verifications effect of the present invention：
Experiment one：
For preparing the preparation method of the cyanate performed polymer of glued membrane：
First, 10Kg bisphenol A cyanate ester monomers are added in 20L stainless steel cauldrons, heating and temperature control is at 80~120 DEG C
Between, cyanate ester monomer is gradually molten into transparency liquid after 2h, obtains liquid cyanate；
2nd, under conditions of temperature is 110~120 DEG C, stirs, add in liquid cyanate and add in batches 1.6Kg
Polysulfone resin (PSU), after 1.5h, during polysulfone resin (PSU) is dissolved completely in cyanate, now system is opaque, homogeneous viscous
Property mixture, add 1.5g polymerization catalysts (preparation method such as specific embodiment six), gathered at 120~130 DEG C
Close reaction；
3rd, after the polyreaction of step 2 carries out 2h, 5g polymerizates are taken every 10min and is placed to release paper
5min, when polyreaction carries out 3.5h, takes Product samples appearance transparent, and feel is flexible and can easily from release paper
Strip down, judge now as polyreaction terminal, cooling, discharging obtain final product the cyanate performed polymer for preparing glued membrane.
After product room temperature is placed 1 week, without cyanate " crystallization is separated out " phenomenon, feel is flexible, ductility is good.
Experiment two：
For preparing the preparation method of the cyanate performed polymer of glued membrane：
First, 10Kg bisphenol A cyanate ester monomers are added in 20L stainless steel cauldrons, is gradually melted between 80~120 DEG C
For transparency liquid, liquid cyanate is obtained；
2nd, under conditions of temperature is 110~120 DEG C, stirs, 2.0Kg polyethersulfone resins are added in liquid cyanate
(PES), it is completely dissolved after 2.0h, 2.0g polymerization catalysts (preparation method such as specific embodiment six) is added, 120~130
Polyreaction is carried out at DEG C；
3rd, after the polyreaction of step 2 carries out 3h, 6g polymerizates are taken every 10min and is placed to release paper
5min, it was observed that product is transparent, and is polymerization when can stripping down from release paper when polyreaction carries out 3.0h
Reaction end, cooling, discharging, obtains final product the cyanate performed polymer for preparing glued membrane.
Experiment three：
For preparing the preparation method of the cyanate performed polymer of glued membrane：
First, 10Kg bisphenol A cyanate ester monomers are added in 20L stainless steel cauldrons, is gradually melted between 80~120 DEG C
For transparency liquid, liquid cyanate is obtained；
2nd, under conditions of temperature is 110~120 DEG C, stirs, 1.5Kg polyether sulphone trees are added in liquid cyanate
Fat (PPSU), is completely dissolved after 1.5h, adds 1.2g polymerization catalysts (preparation method such as specific embodiment six), 120~
Polyreaction is carried out at 130 DEG C；
3rd, after the polyreaction of step 2 carries out 3h, 10 polymerizates are taken every 10min and is placed to release paper
5min, it was observed that product is transparent, and is polymerization when can stripping down from release paper when polyreaction carries out 4.5h
Reaction end, cooling, discharging, obtains final product the cyanate performed polymer for preparing glued membrane.
Claims (7)
1. be used for prepare glued membrane cyanate performed polymer preparation method, it is characterised in that the method is as follows：
First, bisphenol A cyanate ester prepolymer is heated to being completely melt to become homogeneous liquid, obtains liquid cyanate；
2nd, temperature be 110~120 DEG C, stirring under conditions of, in liquid cyanate add thermoplasticity polysulfones resinoid until
Thermoplasticity polysulfones resinoid is completely dissolved, and adds polymerization catalyst, and the addition of polymerization catalyst is the 1 of liquid cyanate quality
~5 ‰, 2~6h of polyreaction is carried out at 120~130 DEG C；
3rd, after the polyreaction of step 2 carries out 2h, take a small amount of polymerizate every 10min and place 5min to release paper,
And it is polyreaction terminal when can stripping down from release paper when observing that product is transparent, cooling, discharging are obtained final product
For preparing the cyanate performed polymer of glued membrane.
2. according to claim 1 be used for prepare glued membrane cyanate performed polymer preparation method, it is characterised in that step one
It is middle to be heated to being completely melt at 80 DEG C~120 DEG C by bisphenol A cyanate ester prepolymer.
3. according to claim 1 be used for prepare glued membrane cyanate performed polymer preparation method, it is characterised in that step 2
Described in polymerization catalyst be acetylacetone copper and 4- nonyl phenols mixture, the wherein matter of acetylacetone copper and 4- nonyl phenols
Amount is than being (1~5):100.
4. according to claim 1,2 or 3 be used for prepare glued membrane cyanate performed polymer preparation method, it is characterised in that step
In rapid two under conditions of temperature is 115 DEG C, stirs, thermoplasticity polysulfones resinoid is added in liquid cyanate until thermoplasticity
Polysulfones resinoid is completely dissolved.
5. according to claim 1,2 or 3 be used for prepare glued membrane cyanate performed polymer preparation method, it is characterised in that step
The addition of polymerization catalyst is 2~the 4 ‰ of liquid cyanate quality in rapid two.
6. according to claim 1,2 or 3 be used for prepare glued membrane cyanate performed polymer preparation method, it is characterised in that step
The addition of polymerization catalyst is the 3 ‰ of liquid cyanate quality in rapid two.
7. according to claim 1,2 or 3 be used for prepare glued membrane cyanate performed polymer preparation method, it is characterised in that step
2~6h of polyreaction is carried out at 125 DEG C in rapid two.
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| CN111500250B (en) * | 2020-05-11 | 2021-08-17 | 四川川环科技股份有限公司 | Preparation method of heat-resistant adhesive |
| CN112048247B (en) * | 2020-09-14 | 2022-04-05 | 黑龙江省科学院石油化学研究院 | Bismaleimide/cyanate ester foamed adhesive film, and preparation method and application thereof |
| CN114806175B (en) * | 2022-04-22 | 2023-04-14 | 川化集团有限责任公司 | Bisphenol A type cyanate ester resin modified polysulfone composite material and preparation method thereof |
| CN115746781B (en) * | 2022-11-22 | 2024-04-16 | 黑龙江省科学院石油化学研究院 | Modified bismaleimide/cyanate adhesive film and preparation method thereof |
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| US6875473B2 (en) * | 2001-01-08 | 2005-04-05 | J. D. Lincoln, Inc. | Woven fabric with a modified ester resin for use as a wet friction liner |
| KR101694138B1 (en) * | 2009-01-19 | 2017-01-09 | 아지노모토 가부시키가이샤 | Resin composition |
| CN101935514B (en) * | 2010-09-30 | 2013-02-20 | 黑龙江省科学院石油化学研究院 | Novel foam structural adhesive and preparation method thereof |
| CN102876268A (en) * | 2012-10-12 | 2013-01-16 | 黑龙江省科学院石油化学研究院 | Phenolic aldehyde type cyanate ester adhesive |
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