CN1861374A - Mehtod for preparing composite material contg. nano-silicon dioxide, polyurethane and cyanate resin - Google Patents
Mehtod for preparing composite material contg. nano-silicon dioxide, polyurethane and cyanate resin Download PDFInfo
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- CN1861374A CN1861374A CN 200510042653 CN200510042653A CN1861374A CN 1861374 A CN1861374 A CN 1861374A CN 200510042653 CN200510042653 CN 200510042653 CN 200510042653 A CN200510042653 A CN 200510042653A CN 1861374 A CN1861374 A CN 1861374A
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- polyurethane
- cyanate ester
- nano silicon
- ester resin
- composite material
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Abstract
A nano-SiO2/polyurethane/cyanate resin composition is prepared through fusing biphenol A type thermosetting cyanate and liquid polyurethane elastomer, mixing, adding nano-SiO2, stirring for homogenizing, ultrasonic oscillating, and solidifying. It has high impact and bending strength and modulus and excellent antiwear, refractory and dielectric properties.
Description
Technical field
The present invention relates to a kind of nano silicon/polyurethane/cyanate ester resin composite material and preparation method thereof, belonging to polymer toughening reinforcement modification field, is the method that adopts liquid urethane elastomer and nano silicon cyanate to be carried out the toughened and reinforced modification of in-situ polymerization specifically.
Background technology
Cyanate ester resin (BCE) is with its excellent dielectric properties, extremely low water absorption rate, high-fire resistance, excellent size stability, good comprehensive mechanical properties and the moulding process close with epoxy resin, enjoy people's favor, become a kind of functional material and the structural material that in fields such as Aero-Space, electronics, have had potentiality since the twentieth century.But, cause its solidfied material more crisp because crosslink density is big after the cyanate ester monomer polymerization.At present the method for cyanate toughening modifying has: with the cyanate copolymerization of single functionality, with the thermosetting resin copolymerization, with the thermoplastic blend, with the rubber elastomer blending and modifying, carry out toughness reinforcingly etc. with inorganic nano-particle, but these methods respectively have its pluses and minuses.The thermosetting resin modified cyanic acid ester resin, little to the toughness raising of resin; High-performance thermoplastic resin modified cyanate ester resin exists manufacturability poor equally, shortcomings such as complicated process of preparation.Use the rubber elastomer modified cyanic acid ester resin, can increase substantially the toughness of modification body, but its intensity can descend to some extent, hear resistance reduces significantly simultaneously; Nanometer particle-modified cyanate ester resin can improve the intensity of resin, but is difficult to improve the toughness of resin, the document announcement inorganic nano-particle is arranged even can reduce the toughness of resin.Adopting liquid urethane elastomer and nano particle that cyanate is carried out toughened and reinforced modification at present, at home and abroad do not appear in the newspapers, is a kind of new modified system.Because polyurethane specific molecule structure and the special surface property of nano particle, not only can improve the toughness of cyanate significantly, can remedy simultaneously intensity and the stable on heating deficiency that elastic body toughening brings again, and can improve wearability and dielectric properties, make its at Aero-Space load-carrying construction spare, involve fields such as stealth material, high-performance electronic printed substrate thoroughly extremely wide application prospect arranged.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes a kind of nano silicon/polyurethane/cyanate ester resin composite material and preparation method thereof.A kind of nano silicon/polyurethane/cyanate ester resin modifier with higher toughness and intensity, excellent hear resistance, wearability and dielectric properties that provides and a kind of direct, simple, pollution-free, applicability is wide, the simple preparation method of operating procedure.
Technical scheme
Technical characterictic of the present invention is:
The composition of raw materials component (by weight) of nano silicon/polyurethane/cyanate ester resin composite material is as follows: 100～150 parts of cyanate ester resins, 1～30 part of polyurethane, 1～5 part of nano silicon.
Described cyanate ester resin is bisphenol A cyanate ester resin (BCE).
Described polyurethane is liquid pfpe type polyurethane elastomer (PUR), and molecular weight is 3000～5000.
Described nano silicon is a kind of multi-cellular structure nano particle, and average grain diameter is 20nm.
A kind of method for preparing above-mentioned nano silicon/polyurethane/cyanate ester resin composite material is characterized in that:
Step 1, with cyanate ester resin and polyurethane at 80～170 ℃ of following melt blendings, add nano silicon, homogeneous stirs 10～60min under this temperature, carries out sonic oscillation 10～60min again, obtains nano silicon/polyurethane/cyanate ester resin prepolymer;
Step 2, nano silicon/polyurethane/cyanate ester resin prepolymer is cured, solidification temperature is controlled at 100～250 ℃, is controlled at 6～12h hardening time, can obtain nano silicon/polyurethane/cyanate ester resin modifier.
Beneficial effect
The invention has the beneficial effects as follows: the present invention adopts a kind of liquid pfpe type polyurethane elastomer and nano silicon that cyanate is carried out toughened and reinforced modification, makes the toughness of this modification body and intensity increase substantially.Impact strength is by 6.0kJ.m
-2Bring up to 8.39～12.4kJ.m
-2, amplification reaches 39.8～106.7%; Bending strength is brought up to 123.0～140.0MPa by 104.0MPa, and amplification reaches 18.3～34.6%.The modification body has excellent dielectric properties, dielectric constant and dielectric loss are respectively 2.85～2.95 and 0.008～0.0150, compare with pure cyanate ester resin, the corresponding increase of the dielectric constant of modification body and dielectric loss, but compare with polyurethane/cyanate modified body, its dielectric constant and dielectric loss reduce.The dielectric properties of modification body still can compare favourably with the modified bismaleimide resin of dielectric properties excellence.The frictional behaviour of modification body has very big raising, changes by 50.0 milligrams/1000 and brings up to 12.0～5.0 milligrams/1000 commentaries on classics, has improved 75～90%.The modification body has excellent hot property, and its heat distortion temperature is brought up to 205.0～210.5 ℃ by 200.0 ℃; Initial heat decomposition temperature is brought up to 390.8～397.5 ℃ by 388.6 ℃; The temperature of maximum weight loss rate correspondence is brought up to 445.0～455.0 ℃ by 435.9 ℃.
Preparation method proposed by the invention in addition stirs in conjunction with homogeneous and supersonic oscillations are disperseed pre-polymerization to mixed system, nano silicon is dispersed in the cyanate matrix better, guarantee the phase structure of polyurethane elastomer in resin simultaneously, increase substantially mechanical property, hot property, dielectric properties of modification body etc.And the situ aggregation method that adopts neither needs solvent, also is not subjected to the restriction of polymer dissolution, is a kind of direct, simple, pollution-free, applicability is wide, operating procedure simply prepares the modified-high polymer body method.
Description of drawings
Fig. 1: the preparation of situ aggregation method modified system and curing process flow chart thereof
The specific embodiment
Now in conjunction with the accompanying drawings the present invention is further described:
Embodiment 1:
10 parts of polyurethane (by weight) and 100 parts of cyanates are mixed under 100 ℃, under this temperature, add 1 part of nano silicon, homogeneous stirs 10min, again through supersonic oscillations 30min, obtains nano silicon/polyurethane/cyanate ester resin prepolymer; Performed polymer is cured, and curing process is 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h, promptly obtains nano silicon/polyurethane/cyanate ester resin modifier.
Embodiment 2:
20 parts of polyurethane (by weight) and 100 parts of cyanates are mixed under 100 ℃, under this temperature, add 3 parts of nano silicons, homogeneous stirs 20min, again through supersonic oscillations 30min, obtains nano silicon/polyurethane/cyanate ester resin prepolymer; Performed polymer is cured, and curing process is 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h,, promptly obtain nano silicon/polyurethane/cyanate ester resin modifier.
Embodiment 3:
30 parts of polyurethane (by weight) and 100 parts of cyanates are mixed under 100 ℃, under this temperature, add 5 parts of nano silicons, homogeneous stirs 30min, again through supersonic oscillations 30min, obtains nano silicon/polyurethane/cyanate ester resin prepolymer; Performed polymer is cured, and curing process is 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h, promptly obtains nano silicon/polyurethane/cyanate ester resin modifier.
Utilize the performance characterization of nano silicon/polyurethane/cyanate ester resin composite material of this method preparation as follows:
1, the mechanical property of composite
The mechanical property of modification body is as shown in table 1.As can be seen, behind different proportioning polyurethane and nano silicon and the cyanate ester resin in-situ polymerization, the mechanical property of modification body all obtains raising by a relatively large margin.
Table 1 nano silicon (SiO
2The mechanical property of)/polyurethane (PUR)/cyanate (BCE) modification body
| Performance | Polyurethane content (part) | S1/PUR/BCE | S3/PUR/BCE | S5/PUR/BCE |
| Impact strength/kJ.m -2 | Pure BCE PUR (10) PUR (20) PUR (30) | 6.0 8.39 11.5 12.1 | 6.0 8.90 12.4 11.3 | 6.0 8.54 12.0 10.9 |
| Bending strength/MPa | Pure BCE PUR (10) PUR (20) PUR (30) | 104 123 126 127 | 104 128 140 128 | 104 135 134 132 |
* s1:SiO
2Content is 1 part, s3:SiO
2Content is 3 parts, s5:SiO
2Content is 5 parts
2, the hot property of composite
The hot property of modification body is as shown in table 2.As can be seen, add polyurethane and nano silicon, the temperature of the heat distortion temperature of modification body, initial heat decomposition temperature and maximum weight loss rate correspondence all increases.
The hot property of table 2 composite
| The modification body | BCE | SiO 2/PUR/BCE |
| Heat distortion temperature ℃ | 200.0 | 207.8 |
| Initial heat decomposition temperature ℃ | 388.6 | 394.5 |
| The temperature of maximum weight loss rate correspondence ℃ | 435.9 | 451.6 |
3, the dielectric properties of composite
The dielectric properties of modification body are as shown in table 3.As can be seen, after adding polyurethane and nano silicon, the dielectric constant of modification body and dielectric loss slightly increase than pure cyanate, but compare with polyurethane/cyanate modified body, and dielectric constant and dielectric loss reduce.And can compare favourably with the modified bismaleimide resin of dielectric properties excellence.
The dielectric properties of table 3 composite
| DIELECTRIC CONSTANTS | Dielectric loss angle tangent Tan δ | |
| BCE | 2.80 | 0.0070 |
| SiO 2/PUR/BCE | 2.93 | 0.0114 |
| PUR/BCE | 2.98 | 0.0120 |
| 4501A 4503A | 2.94 2.95 | 0.0117 0.0118 |
* 4501A and 4503A are and report bi-maleimide modified body
Nano silicon/polyurethane after the modification/cyanate ester resin modifier can be widely used in numerous areas such as making electronic circuit printed panel, aerospace structural members, radome, communications satellite.
Claims (5)
1. nano silicon/polyurethane/cyanate ester resin composite material, it is characterized in that: composition of raw materials component (by weight) is: 100～150 parts of cyanate ester resins, 1～30 part of polyurethane, 1～5 part of nano silicon.
2. nano silicon/polyurethane according to claim 1/cyanate ester resin composite material is characterized in that: described cyanate ester resin is bisphenol A cyanate ester resin (BCE).
3. nano silicon/polyurethane according to claim 1/cyanate ester resin composite material is characterized in that: described polyurethane is liquid pfpe type polyurethane elastomer (PUR), and molecular weight is 3000～5000.
4. nano silicon/polyurethane according to claim 1/cyanate ester resin composite material is characterized in that: described nano silicon is a kind of multi-cellular structure nano particle, and average grain diameter is 20nm.
5. method for preparing above-mentioned nano silicon/polyurethane/cyanate ester resin composite material is characterized in that:
Step 1, with cyanate ester resin and polyurethane at 80～170 ℃ of following melt blendings, add nano silicon, homogeneous stirs 10～60min under this temperature, carries out sonic oscillation 10～60min again, obtains nano silicon/polyurethane/cyanate ester resin prepolymer;
Step 2, nano silicon/polyurethane/cyanate ester resin prepolymer is cured, solidification temperature is controlled at 100～250 ℃, is controlled at 6～12h hardening time, can obtain nano silicon/polyurethane/cyanate ester resin modifier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100426537A CN100519154C (en) | 2005-05-10 | 2005-05-10 | Mehtod for preparing composite material contg. nano-silicon dioxide, polyurethane and cyanate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100426537A CN100519154C (en) | 2005-05-10 | 2005-05-10 | Mehtod for preparing composite material contg. nano-silicon dioxide, polyurethane and cyanate resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1861374A true CN1861374A (en) | 2006-11-15 |
| CN100519154C CN100519154C (en) | 2009-07-29 |
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| CNB2005100426537A Expired - Fee Related CN100519154C (en) | 2005-05-10 | 2005-05-10 | Mehtod for preparing composite material contg. nano-silicon dioxide, polyurethane and cyanate resin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250338B (en) * | 2008-04-01 | 2010-11-10 | 中国科学院化学研究所 | Modified inorganic nano-particle as well as preparation method and use thereof |
| CN101450994B (en) * | 2007-11-30 | 2011-02-02 | 江都市吴桥树脂厂 | Method for preparing cyanate ester resin prepolymer |
| CN102718942A (en) * | 2012-06-13 | 2012-10-10 | 华东理工大学 | Preparation of wear-resistant and yellowing-resistant polyurethane resin and application thereof |
| CN109476924A (en) * | 2016-07-20 | 2019-03-15 | 日立化成株式会社 | Hot curing resin composition, layer insulation resin film, composite membrane, printed wiring board and its manufacturing method |
| CN110467816A (en) * | 2019-08-19 | 2019-11-19 | 何永明 | A kind of toughening cyanate resin base composite material |
| CN113214622A (en) * | 2021-05-14 | 2021-08-06 | 安徽安车新材料有限公司 | Alloy resin and glass fiber reinforced plastic plate using same |
-
2005
- 2005-05-10 CN CNB2005100426537A patent/CN100519154C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450994B (en) * | 2007-11-30 | 2011-02-02 | 江都市吴桥树脂厂 | Method for preparing cyanate ester resin prepolymer |
| CN101250338B (en) * | 2008-04-01 | 2010-11-10 | 中国科学院化学研究所 | Modified inorganic nano-particle as well as preparation method and use thereof |
| CN102718942A (en) * | 2012-06-13 | 2012-10-10 | 华东理工大学 | Preparation of wear-resistant and yellowing-resistant polyurethane resin and application thereof |
| CN109476924A (en) * | 2016-07-20 | 2019-03-15 | 日立化成株式会社 | Hot curing resin composition, layer insulation resin film, composite membrane, printed wiring board and its manufacturing method |
| CN109476924B (en) * | 2016-07-20 | 2022-02-18 | 昭和电工材料株式会社 | Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board, and method for producing same |
| US11827789B2 (en) | 2016-07-20 | 2023-11-28 | Resonac Corporation | Thermosetting resin composition, interlayer insulation resin film, composite film, printed wiring board, and production method thereof |
| CN110467816A (en) * | 2019-08-19 | 2019-11-19 | 何永明 | A kind of toughening cyanate resin base composite material |
| CN113214622A (en) * | 2021-05-14 | 2021-08-06 | 安徽安车新材料有限公司 | Alloy resin and glass fiber reinforced plastic plate using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100519154C (en) | 2009-07-29 |
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