CN102167822A - Cyanate/microcapsule resin system and preparation method thereof - Google Patents
Cyanate/microcapsule resin system and preparation method thereof Download PDFInfo
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- CN102167822A CN102167822A CN2011100512909A CN201110051290A CN102167822A CN 102167822 A CN102167822 A CN 102167822A CN 2011100512909 A CN2011100512909 A CN 2011100512909A CN 201110051290 A CN201110051290 A CN 201110051290A CN 102167822 A CN102167822 A CN 102167822A
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Abstract
The invention discloses a cyanate/microcapsule resin system and a preparation method thereof. The preparation method is as follows: calculated by weight, 100 parts of cyanate (CE) is heated at 80-100 DEG C to melt, organotin microcapsule coated with 0.125-5 parts of polyurea formaldehyde is filled in CE resin; and by utilizing the controlled-release function of the polyurea formaldehyde used as the microcapsule wall material to the organotin compound used as the microcapsule core catalyst, the CE curing reaction temperature and reaction rate can be adjusted. After being cured, the obtained CE/microcapsule resin system has good mechanical properties; and the resin system can be used to prepare high-performance composites used in aviation and aerospace, electronic elements and the like.
Description
Technical field
The present invention relates to a kind of cyanate ester resin system and preparation method thereof.Be specifically related to a kind of Uramite coated organotin compound microcapsule is filled into the cyanate ester resin system, the slow releasing function of its core materials is regulated a kind of novel cyanate ester resin system of cyanate ester resin speed of reaction and preparation method thereof by microcapsule, belonged to the high performance composite field.
Background technology
Cyanate (CE) resin is the novel high-performance thermosetting resin of a class of the exploitation eighties with 26S Proteasome Structure and Function, and monomer whose contains two or more cyanates (OCN) functional group.Because the CE resin has special structure and reactivity, therefore its cured article has a series of outstanding advantages, as dielectric properties, low-down specific inductivity (e=2.6～3.2) and the dielectric loss (tgd=0.001～0.008) etc. of high heat resistance, low rate of moisture absorption, excellence.Therefore the CE resin has great potential at aspects such as military affairs, Aeronautics and Astronautics, navigation, electronic devices and components.At present, the CE resin is considered to prepare the high-performance thermosetting resin of the tool application potential in structure/function integration material aspect.
Although the CE resin has the excellent comprehensive performance, it is used and still to be subjected to very big restriction, the monomeric curing reaction temperature height of CE wherein, and long reaction time is one of its main drawback.This shortcoming causes the cured article unrelieved stress big, and is in use easily destroyed, the service reliability variation of material.We know that for thermosetting resin, the curing process of resin is most important, because it directly determines the structure and the degree of crosslinking of resin curing cross-linked network, thus the final performance of decision material.Therefore, for improving the curing process of CE, people have carried out number of research projects, add the solidification value that catalyzer can obviously reduce CE usually, improve curing reaction speed.Result of study shows that organo-tin compound etc. are the effective catalysts of CE.But for CE, the adding of catalyzer but causes new problem, and promptly curing reaction speed is fast, and the resin solidification degree is inhomogeneous, the especially intensity reduction etc. of the performance of cured article.Obviously, how effectively to reduce CE curing reaction temperature and effectively slow down CE curing reaction speed and use significant for expanding the CE resin.
Summary of the invention
The object of the present invention is to provide a kind of curing reaction temperature and speed of reaction controlled, have cyanate ester resin system of excellent mechanical performances and preparation method thereof after the curing.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of cyanate ester resin system, with b is weight unit, cyanate fusion under 80～100 ℃ temperature with 100b, the Uramite coated organotin compound microcapsule that adds 0.125～5b, under 100～120 ℃ temperature and agitation condition, reacted 30～120 minutes, obtain containing the cyanate prepolymerization system of microcapsule; Inject this system through preheating and scribble the mould of releasing agent, after the vacuum outgas, be cured processing by 120 ℃ of technologies/2h+150 ℃/2h+180 ℃/2h+200 ℃/2h again.
Uramite coated organotin compound microcapsule of the present invention, for the Chinese invention patent of publication number for CN 101580624 provides, its preparation method is for adopting situ aggregation method, with urea, formaldehyde is the main wall material raw material, with the catalyzer organo-tin compound is main capsule-core raw material, with water is reaction medium, select different types of tensio-active agent, by controlling certain rotating speed, the pH value of conditioned reaction solution system is 4～5, temperature of reaction is reacted after 2～4 hours at 30～50 ℃, the synthetic Uramite coated organotin compound microcapsule that obtains; Reaction product is obtained the microcapsule particle of white after water/washing with acetone, suction filtration, drying.Its organo-tin compound is dibutyl tin laurate or dibutyl tin laurate-cyanate esters; Described Uramite coated organotin compound microcapsule, its particle diameter are 0.5～1000 μ m, and wall thickness is 0.1～60 μ m.
By a kind of cyanate ester resin system that preparation method of the present invention obtains, its raw material is formed and proportioning is: cyanate 100b, Uramite coated organotin compound microcapsule 0.125 ~ 5b, b are weight unit.
Microcapsule are to utilize film forming material to coat the fine particle that forms a kind of " nuclear-shell " structure having dispersed solid matter, liquid or gas, and it can play functions such as protection, sustained release to capsule-core.Compared with prior art, the present invention utilizes the slow releasing function of cyst material uramit to capsule-core catalyzer organo-tin compound, realizes the adjusting to CE curing reaction temperature and speed of reaction.The CE/ microcapsule resin system that obtains has the good mechanical performance after solidifying, and this resin system can be used for preparing aerospace high performance composite, electron device etc.
Specific implementation method
Embodiment one
By publication number is Chinese invention patent " Uramite coated organotin compound microcapsule and the preparation method " technical scheme of CN101580624, obtaining particle diameter is 0.5～1000 μ m, wall thickness 0.1～60 μ m, the Uramite coated organotin compound microcapsule of capsule-core content about 60%, its organo-tin compound are dibutyl tin laurate, dibutyl tin laurate-cyanate.
Take by weighing 100g4,4 '-two cyanate ester based diphenyl propanes are in the 250ml beaker, behind 100 ℃ of following heating and meltings, adding median size is the uramit coating dibutyl tin laurate-4 of 150 μ m, 4 '-two cyanate ester based diphenyl propane compound microcapsule 0.125,0.25,0.5,5g, under the agitation condition at 100 ~ 120 ℃ of pre-polymerization certain hours, obtain containing the CE prepolymerization system of microcapsule, inject above-mentioned system through preheating and scribble the mould of releasing agent, in 90 ~ 100 ℃ of following vacuum outgas 30min, be cured by 120 ℃ of technologies/2h+150 ℃/2h+180 ℃/2h+200 ℃/2h.With the material test performance after being cut into desired size on the cutting machine for preparing.Relevant performance data sees Table 1.The reactivity of the cyanate that table 1 provides for present embodiment (CE)/microcapsule resin system and CE/ microcapsule resin system solidify the back performance.In the table, 1, gel time records in air atmosphere with the dull and stereotyped little skill in using a kitchen knife in cookery; 2, the reaction summit temperature is to obtain by the DSC curve, and temperature rise rate is 10 ℃/min, sample pool N
2Flow velocity is 50ml/min.
Table 1
| 150 μ m microcapsule content (wt%) | 120 ℃ of gel times (min) 1 | The reaction summit temperature (℃) 2 | Flexural strength (MPa) | Shock strength (kJ/m 2） |
| 0 | / | 320 | / | / |
| 0.125 | 153 | 282 | 135 | 10.0 |
| 0.25 | 98 | 260 | 131 | 10.2 |
| 0.5 | 60 | 245 | 128 | 10.6 |
| 5 | 30 | 150 | 111 | 13.0 |
As can be seen from Table 1, in CE, add the dibutyl tin laurate-4 that 150 μ m uramits coat, behind 4 '-two cyanate ester based diphenyl propane compound microcapsule, the temperature of reaction of resin system reduces, and increase gradually along with microcapsule content, the gel time of resin system and reaction summit temperature reduce gradually, the adding of these these microcapsule of explanation different content can be regulated the CE resin reaction by slow release capsule-core, and the CE/ microcapsule resin system after solidifying has the good mechanical performance.
Embodiment two
Take by weighing 100g4,4 '-two cyanate ester based diphenyl propanes are in the 250ml beaker, behind 100 ℃ of following heating and meltings, adding median size is uramit coating dibutyl tin laurate compound microcapsule 0.125,0.25, the 0.5g of 150 μ m, under the agitation condition at 100 ~ 120 ℃ of pre-polymerization certain hours, obtain containing the CE prepolymerization system of microcapsule, inject above-mentioned system through preheating and scribble the mould of releasing agent, in 90 ~ 100 ℃ of following vacuum outgas 30min, be cured by 120 ℃ of technologies/2h+150 ℃/2h+180 ℃/2h+200 ℃/2h.With the material test performance after being cut into desired size on the cutting machine for preparing.The cyanate that table 2 provides for present embodiment (CE)/microcapsule resin system reactivity and CE/ microcapsule resin system solidify the back performance.
Table 2
| 150 μ m microcapsule content (wt%) | 120 ℃ of gel times (min) 1 | The reaction summit temperature (℃) 2 | Flexural strength (MPa) | Shock strength (kJ/m 2） |
| 0 | / | 320 | / | / |
| 0.125 | 120 | 270 | 139 | 9.6 |
| 0.25 | 78 | 252 | 134 | 9.8 |
| 0.5 | 40 | 234 | 128 | 10 |
As can be seen from Table 2, after in CE, adding the dibutyl tin laurate compound microcapsule of 150 μ m uramits coating, the temperature of reaction of resin system reduces, and increase gradually along with microcapsule content, the gel time of resin system and reaction summit temperature reduce gradually, the adding of these these microcapsule of explanation different content can be regulated the CE resin reaction by slow release capsule-core, and the CE/ microcapsule resin system after solidifying has the good mechanical performance.
Embodiment three
Take by weighing 100g4,4 '-two cyanate ester based diphenyl propanes are in the 250ml beaker, behind 100 ℃ of following heating and meltings, adding median size is uramit coating dibutyl tin laurate compound microcapsule 0.125,0.25, the 0.5g of 20 μ m, under the agitation condition at 100 ~ 120 ℃ of pre-polymerization certain hours, obtain containing the CE prepolymerization system of microcapsule, inject above-mentioned system through preheating and scribble the mould of releasing agent, in 90 ~ 100 ℃ of following vacuum outgas 30min, be cured by 120 ℃ of technologies/2h+150 ℃/2h+180 ℃/2h+200 ℃/2h.With the material test performance after being cut into desired size on the cutting machine for preparing.The cyanate that table 3 provides for present embodiment (CE)/microcapsule resin system reactivity and CE/ microcapsule resin system solidify the back performance.
Table 3
| 50 μ m microcapsule content (wt%) | 120 ℃ of gel times (min) 1 | The reaction summit temperature (℃) 2 | Flexural strength (MPa) | Shock strength (kJ/m 2） |
| 0 | / | 320 | / | / |
| 0.125 | 189 | 278 | 136 | 10.3 |
| 0.25 | 124 | 263 | 123 | 10.8 |
| 0.5 | 96 | 250 | 114 | 12.0 |
As can be seen from Table 3, after in CE, adding the dibutyl tin laurate compound microcapsule of 50 μ m uramits coating, the temperature of reaction of resin system reduces, and increase gradually along with microcapsule content, the gel time of resin system and reaction summit temperature reduce gradually, the adding of these explanation different content microcapsule can be regulated the CE resin reaction by slow release capsule-core, and the CE/ microcapsule resin system after solidifying has the good mechanical performance.
Claims (4)
1. the preparation method of a cyanate ester resin system, it is characterized in that: be weight unit with b, cyanate fusion under 80～100 ℃ temperature with 100b, the Uramite coated organotin compound microcapsule that adds 0.125～5b, under 100～120 ℃ temperature and agitation condition, reacted 30～120 minutes, and obtained containing the cyanate prepolymerization system of microcapsule; Inject this system through preheating and scribble the mould of releasing agent, after the vacuum outgas, be cured processing by 120 ℃ of technologies/2h+150 ℃/2h+180 ℃/2h+200 ℃/2h again.
2. the preparation method of a kind of cyanate ester resin system according to claim 1, it is characterized in that: described Uramite coated organotin compound microcapsule, its organo-tin compound are dibutyl tin laurate or dibutyl tin laurate-cyanate esters.
3. the preparation method of a kind of cyanate ester resin system according to claim 1 is characterized in that: described Uramite coated organotin compound microcapsule, its particle diameter are 0.5～1000 μ m, and wall thickness is 0.1～60 μ m.
4. a kind of cyanate ester resin system that adopts claim 1 preparation method to obtain is characterized in that: raw material is formed and proportioning is cyanate 100b, and Uramite coated organotin compound microcapsule 0.125 ~ 5b, b are weight unit.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104694069A (en) * | 2014-12-31 | 2015-06-10 | 黑龙江省科学院石油化学研究院 | Intermediate-temperature-cured cyanate ester foamed structural adhesive and preparation method thereof |
| CN111171353A (en) * | 2020-01-17 | 2020-05-19 | 中国航空工业集团公司济南特种结构研究所 | Latent catalyst and preparation method of cyanate resin prepreg |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467244A (en) * | 2003-03-07 | 2004-01-14 | 梁国正 | Organic tin compound for cyanate ester resin curing reaction and method for preparing the same |
| CN101323663A (en) * | 2008-07-16 | 2008-12-17 | 苏州大学 | Catalytic composite used for ethylene rhodanate resin curing and preparation thereof |
| CN101580624A (en) * | 2009-04-30 | 2009-11-18 | 苏州大学 | Uramite coated organotin compound microcapsule and preparation method thereof |
-
2011
- 2011-03-03 CN CN2011100512909A patent/CN102167822A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467244A (en) * | 2003-03-07 | 2004-01-14 | 梁国正 | Organic tin compound for cyanate ester resin curing reaction and method for preparing the same |
| CN101323663A (en) * | 2008-07-16 | 2008-12-17 | 苏州大学 | Catalytic composite used for ethylene rhodanate resin curing and preparation thereof |
| CN101580624A (en) * | 2009-04-30 | 2009-11-18 | 苏州大学 | Uramite coated organotin compound microcapsule and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104694069A (en) * | 2014-12-31 | 2015-06-10 | 黑龙江省科学院石油化学研究院 | Intermediate-temperature-cured cyanate ester foamed structural adhesive and preparation method thereof |
| CN111171353A (en) * | 2020-01-17 | 2020-05-19 | 中国航空工业集团公司济南特种结构研究所 | Latent catalyst and preparation method of cyanate resin prepreg |
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Application publication date: 20110831 |