CN1376736A - Process for preparing polysiloxanel alkyl poly(methyl)acrylate as damping material - Google Patents
Process for preparing polysiloxanel alkyl poly(methyl)acrylate as damping material Download PDFInfo
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- CN1376736A CN1376736A CN 01107285 CN01107285A CN1376736A CN 1376736 A CN1376736 A CN 1376736A CN 01107285 CN01107285 CN 01107285 CN 01107285 A CN01107285 A CN 01107285A CN 1376736 A CN1376736 A CN 1376736A
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Abstract
A damping polysiloxane/alkyl poly(methyl)acrylate material is prepared from alpha, omega-dihydroxy polysiloxane oligomer, alkyl poly(methyl)acrylate, cross-linking agent, catalyst and trigger through proportioning, stirring at 0-60 deg.C under existance of nitrogen gas, loading in mould, and reacting at 60-90 deg.C and 0-5 MPa or in vacuum oven for 24 hr.
Description
The present invention relates to the preparation method of a kind of polysiloxane/poly-(methyl) alkyl acrylate damping material, belong to Polymer Synthesizing and forming process field thereof.
Polymer materials under external force, when sub-chain motion is obstructed when being in half hysteretic state, the rubbing effect that is produced is converted into thermal dissipation with mechanical energy and falls.Polymer damping material utilizes this principle just, reaches the purpose of vibration and noise reducing.At the glass transition region of polymkeric substance, macromolecular material has maximum damping action to vibration, and obviously, the width of superpolymer glass transition region has determined the size in damping material effective efficiency district.By the homopolymer that a kind of monomer is formed, glass transition region is very narrow, generally only has 20～30 ℃.Therefore, by copolymerization, blend particularly interpenetrating polymer networks obtain wide temperature (wideband) damping material, make it to be adapted to use down at all temps (frequency), be damping material and the technology thereof competitively researched and developed of countries in the world in recent years.
About preparing damping material with interpenetrating polymer networks, past concentrates on urethane and the Vinylite mostly, these interpenetrating polymer networks often can produce the very wide damping material in a kind of effective efficiency district, but its thermotolerance and antioxidant property and polysiloxane/polypropylene ester damping material differs greatly.Polymer, 1992, Vol.33, NO.4, with Polymer 1989, reported on the Vol.30 that X.We.He uses the room temperature vulcanized silicone rubber technology, adopts hydroxy-end capped polydimethylsiloxane oligopolymer (PDMS) to combine with the radical polymerization system of methacrylic ester methyl ester, carry out PDMS/PMMA and pass through mutually synchronously, make transparent or semitransparent mould material.This material gas transmitance is very high, and PMMA improves very big to the silicon rubber mechanical property.Only add 30% PMMA, then silicon rubber is had tangible enhancement.But because the uncompatibility of PDMS and most polymers, above-mentioned interpenetrating polymer networks material has coarse phase structure, and its disperse phase phase farmland is generally tens millimicrons, and goes up two transformation peaks of appearance in differential scanning calorimeter (DSC).Obviously, this polymkeric substance complementary networks (IPN) material can not be as damping material.U.S. DowCorning company patent 2 in french application in 1998,757,528, announced by the α that contains aminomethyl phenyl, alpha, omega-dihydroxy polysiloxane oligomer and polyhydroxy siloxane linking agent form first network, and methyl methacrylate (phenyl ester) forms second network with its linking agent and constitutes IPN; The main purpose of this patent is that preparation is transparent, and the optical material that refractive index is high had not both been mentioned the application of material aspect vibration and noise reducing in full, does not also have the test data of report about the material damping aspect of performance.
The objective of the invention is to provide the preparation method of a kind of polysiloxane/poly-(methyl) alkyl acrylate damping material at the deficiencies in the prior art, being characterized in introducing in the IPN material polysiloxane widens the low temperature damping district of poly-(methyl) alkyl acrylate and improves its thermotolerance, and improve the damping value of polysiloxane with poly-(methyl) alkyl acrylate, thereby it is wide and tg δ value is higher and the damping material that can regulate to obtain a kind of leap temperature range of glass transition region.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The preparation method of polysiloxane/poly-(methyl) alkyl acrylate damping material;
A. the preparation of polysiloxane
To contain the precursor of methylphenyl siloxane and octamethylcyclotetrasiloxane as starting raw material, mol ratio with methylphenyl siloxane modular construction and dimethyl siloxane units structure is 6～99: 94～1, Tetramethylammonium hydroxide is 0.01～0.1% of a siloxanes gross weight, add and have agitator, in the reactor of thermometer and condenser, in 90～120 ℃ of temperature, feeding pressure is 0.1330～0.4081MPa water vapor, after treating that viscosity increases, balanced reaction 2～4 hours, be warming up to 170 ℃ of decomposition and touched coal 0.5～1 hour, stop to feed water vapor, change logical nitrogen and removed low-molecular material 2 hours, obtain weight-average molecular weight M
w=400～50000 α, the end capped polysiloxane oligomer of alpha, omega-dihydroxy, its structural table is shown
R
1，R
3＝，
，-CH
3，R
2，R
4＝-CH
3
B. synchronous preparation method of passing through damping material mutually
With 20～80 parts of α, alpha, omega-dihydroxy polysiloxane oligomer, 1～4 part of 1～5 part of methyl silicate or tetraethoxy and catalyzer, add and have in the reactor of stirring, with 80～20 parts in the mixture of alkyl methacrylate or it and alkyl acrylate, 0.2～1 part of initiator, 0～8 part of linking agent, add in the above-mentioned same reactor that has a stirring, under nitrogen atmosphere, mix with α, alpha, omega-dihydroxy polysiloxane oligomer, in 60～90 ℃ of reactions of temperature 24 hours, obtain the interpenetrating polymer networks damping material at a glass transition peak.
The precursor that contains methylphenyl siloxane is an aminomethyl phenyl dihydroxyl silane, and trimethyl triphenyl cyclotrisiloxane and/or tetramethyl tetraphenyl cyclotetrasiloxane are at least a.
Catalyzer is a diethyl oxalic acid tin, dioctyl oxalic acid tin, and dibutyl tin acetate, dioctyl two lauric acid tin and/or stannous octoate are at least a.
Alkyl methacrylate is a methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate; Alkyl acrylate is a 2-EHA, vinylformic acid lauryl alcohol ester, and butyl acrylate, ethyl propenoate and/or methyl acrylate are at least a.
Linking agent is a dimethacrylate TEG ester, diacrylate one condensed ethandiol ester, and diacrylate triglycerin ester, 1.1.1-Viscoat 295 and/or Vinylstyrene are at least a.
Initiator is an azobisisobutyronitrile, and dibenzoyl peroxide and/or peroxy dicarbonate are at least a.
The DMA test-results shows, the a series of polysiloxane that the make/poly-synchronous interpenetrating polymer networks damping material of (methyl) alkyl acrylate, the glass transition peak that all has a Gao Erkuan, the leap temperature of its glass transition region can reach 110～155 ℃, high damping value tg δ
MaxCan reach 1.4～0.55, and can in-95～+ 130 ℃ temperature range, regulate; DSC shows that material eliminated the crystallization-melting peak of polydimethylsiloxane fully, but segment do not ossify, and can make softness or harder material, has mechanical property preferably; Thermal weight loss (TGA) shows that material has superior thermotolerance, improves with PMPS content, and the initial heat decomposition temperature of material can improve 50～100 ℃ on the basis of virgin pp acid alkyl ester, obviously reduces as weight loss rate after greater than 400 ℃ at high temperature especially.
This polymer damping material can be widely used in aerospace, aircraft, launch vehicle, satellite, bullet train, and precision instrument and Architectural Equipment aspect have remarkable economic efficiency and social benefit.
The present invention has following advantage
1. in the presence of water vapor, preparation α, alpha, omega-dihydroxy tolyl polysiloxane oligomer, particularly utilize the dihydroxyl aminomethyl phenyl silane in polysiloxane oligomer, directly to introduce the aminomethyl phenyl chain link, be that the inventor creates first, saved the step of preparation and purification aminomethyl phenyl cyclosilane, simplify technology, reduced cost.
2. the oligopolymer of hydroxy-end capped poly-(dimethyl siloxane/methylphenyl siloxane) random copolymerization that makes has been eliminated the crystallinity of polydimethylsiloxane (PDMS) fully, has improved tg δ value under the low temperature.But segment does not ossify.As required, the initial second-order transition temperature of polysiloxane/polyacrylic ester IPN material can reach-95 ℃, and terminal temperature can reach 130 ℃, has reached the purpose that has the high damping value in broad temperature territory.
3. with common raw material and linking agent, prepare damping material, help its forming process and further suitability for industrialized production by synchronous interpenetrating polymer networks technology.The more important thing is by regulating the catalyzer and the dosage of crosslinking agent of monomer and oligopolymer, regulate the relative response speed of two kinds of compositions, the microphase-separated degree of effective control material, improve the consistency of two base polymers, rather than the linking agent or the monomer that add certain special construction reach this purpose, is a kind of effective ways with preparation IPN polymer as damping material of theory significance and actual value.
4. except having wide and high damping value, material itself also has high heat-resisting and oxidative stability, weathering resistance, water-fast vapour permeability and oil resistance etc.Application prospect is very wide.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
1～3, be the preparation of α, alpha, omega-dihydroxy methylsiloxane oligopolymer, concrete recipe ingredient (wherein said raw material umber is parts by weight except that specified otherwise), detailed being shown in Table 1.
Press the recipe ingredient of table 1, respectively aminomethyl phenyl dihydroxyl silane and octamethylcyclotetrasiloxane and alkali glue [are contained (CH
3)
4NOH 2%] add and to have in the reactor of agitator, thermometer, condenser and gas inlet-outlet, to start stirrings, be warming up to 110～120 ℃, when treating that viscosity increases, feeding pressure is the water vapor of 0.1330～0.4081MPa, reacts 2～3 hours.Be warming up to 170 ℃, react to decompose in 0.5～1 hour and touch coal, stop to feed water vapor, change logical nitrogen 2 hours, remove low-molecular material.Stop heating and logical nitrogen, obtain α, the end capped polysiloxane oligomer of alpha, omega-dihydroxy, record weight-average molecular weight M through gel permeation chromatography
w=4000～20000.
4～6 is the preparation of synchronous interpenetrating polymer networks, and concrete recipe ingredient is detailed to be shown in Table 2.
Press the recipe ingredient of table 2; mixture, dimethacrylate TEG ester and Diisopropyl azodicarboxylate with α, alpha, omega-dihydroxy polysiloxane oligomer, tetraethoxy, stannous octoate and alkyl methacrylate thereof or it and alkyl acrylate adds in the reactor respectively; under nitrogen protection, 0～60 ℃ mixes and is cast in the mould.Reinforced mould is placed on the press of 0～5MPa or vacuum drying oven, follow procedure heats up as 65 ℃, 4 hours; 70 ℃, 6 hours; 75 ℃, 12 hours; 90 ℃, 2 hours; Obtain synchronous interpenetrating polymer networks damping material.
Comparative example is that α, alpha, omega-dihydroxy polysiloxane oligomer are mixed with tetraethoxy and stannous octoate, at room temperature keeps 24 hours, treat cross moulding after, add Diisopropyl azodicarboxylate, dimethacrylate TEG ester, methyl methacrylate is dipped to predetermined weight, at the same terms, press 70 ℃, 4 hours then, 80 ℃, 4 hours, 90 ℃, 2 hours, compacting makes, and shows two Tg peaks on DMA.
The recipe ingredient of table 1 preparation α, alpha, omega-dihydroxy polysiloxane oligomer
The synchronous interpenetrating polymer networks recipe ingredient of table 2 preparation
Claims (6)
1. the preparation method of polysiloxane/poly-(methyl) alkyl acrylate damping material is characterized in that:
A. the preparation of polysiloxane
To contain the precursor of methylphenyl siloxane and octamethylcyclotetrasiloxane is 6～99: 94～1 as starting raw material with the mol ratio of methylphenyl siloxane modular construction and dimethyl siloxane units structure, Tetramethylammonium hydroxide is 0.01%～0.1% of a siloxanes total amount, add and have agitator, in the reactor of thermometer and condenser, in 90 ℃～120 ℃ of temperature, after treating that viscosity increases, feeding pressure is the water vapor of 0.1330～0.4081MPa, balanced reaction 2～4 hours, be warming up to 170 ℃ of decomposition and touched coal 0.5～1 hour, stop to feed water vapour, change logical nitrogen and removed low-molecular material 2 hours, obtain weight-average molecular weight M
w=400～50000 α, the end capped polysiloxane oligomer of alpha, omega-dihydroxy, its structural table is shown
R
1，R
3＝，
，-CH
3，R
2，R
4＝-CH
3
B. synchronous preparation method of passing through damping material mutually
With α, (wherein said raw material umber is except that specified otherwise for the alpha, omega-dihydroxy polysiloxane oligomer, the umber of all attaching most importance to) 20～80 part, 1～4 part of 1～5 part of methyl silicate or tetraethoxy and catalyzer, add and have in the reactor of stirring, with 80～20 parts in the mixture of alkyl methacrylate or it and alkyl acrylate, 0.2～1 part of initiator, 0～8 part of linking agent, add in the above-mentioned same reactor that has a stirring, under nitrogen atmosphere with α, the alpha, omega-dihydroxy polysiloxane oligomer is mixed, in 0～60 ℃ of temperature, mix and be cast in the mould, again the mould that will feed in raw material place on the press of 0～5MPa or vacuum drying oven in 60～90 ℃ of reactions of temperature 24 hours, obtain the interpenetrating polymer networks damping material at a glass transition peak.
2. according to the preparation method of the described polysiloxane of claim 1/poly-(methyl) alkyl acrylate damping material, the precursor that it is characterized in that containing methylphenyl siloxane is an aminomethyl phenyl dihydroxyl silane, and trimethyl triphenyl cyclotrisiloxane and/or tetramethyl tetraphenyl cyclotetrasiloxane are at least a.
3. according to the preparation method of the described polysiloxane of claim 1/poly-(methyl) alkyl acrylate damping material, it is characterized in that catalyzer is a diethyl oxalic acid tin, dioctyl oxalic acid tin, dibutyl tin acetate, dioctyl two lauric acid tin and/or stannous octoate are at least a.
4. according to the preparation method of the described polysiloxane of claim 1/poly-(methyl) alkyl acrylate damping material, it is characterized in that alkyl methacrylate is a methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate; Alkyl acrylate is a butyl acrylate, 2-EHA, and vinylformic acid lauryl alcohol ester, ethyl propenoate and/or methyl acrylate are at least a.
5. according to the preparation method of the described polysiloxane of claim 1/poly-(methyl) alkyl acrylate damping material, it is characterized in that linking agent is, dimethacrylate TEG ester, diacrylate one condensed ethandiol ester, diacrylate two glycerine ester that contracts, 1.1.1-Viscoat 295 and/or Vinylstyrene are at least a.
6. according to the preparation method of the described polysiloxane of claim 1/poly-(methyl) alkyl acrylate damping material, it is characterized in that initiator is a Diisopropyl azodicarboxylate, dibenzoyl peroxide and/or peroxy dicarbonate are at least a.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011072857A CN1167743C (en) | 2001-03-27 | 2001-03-27 | Process for preparing polysiloxanel alkyl poly(methyl)acrylate as damping material |
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|---|---|---|---|
| CNB011072857A CN1167743C (en) | 2001-03-27 | 2001-03-27 | Process for preparing polysiloxanel alkyl poly(methyl)acrylate as damping material |
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| CN1376736A true CN1376736A (en) | 2002-10-30 |
| CN1167743C CN1167743C (en) | 2004-09-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725866A (en) * | 2014-12-17 | 2015-06-24 | 苏州锦腾电子科技有限公司 | High-damping silicon rubber |
| CN106496450A (en) * | 2016-09-30 | 2017-03-15 | 深圳航天科技创新研究院 | A kind of stress response type polymethyl methacrylate modified silicon boron polymer microgel and preparation method thereof |
| CN108530659A (en) * | 2018-05-17 | 2018-09-14 | 苏州大学 | A kind of polyphenylene ether-poly siloxanes photo-crosslinking film and preparation method thereof based on graft copolymer |
-
2001
- 2001-03-27 CN CNB011072857A patent/CN1167743C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725866A (en) * | 2014-12-17 | 2015-06-24 | 苏州锦腾电子科技有限公司 | High-damping silicon rubber |
| CN106496450A (en) * | 2016-09-30 | 2017-03-15 | 深圳航天科技创新研究院 | A kind of stress response type polymethyl methacrylate modified silicon boron polymer microgel and preparation method thereof |
| CN106496450B (en) * | 2016-09-30 | 2018-11-27 | 深圳航天科技创新研究院 | A kind of stress response type polymethyl methacrylate modified silicon boron polymer microgel and preparation method thereof |
| CN108530659A (en) * | 2018-05-17 | 2018-09-14 | 苏州大学 | A kind of polyphenylene ether-poly siloxanes photo-crosslinking film and preparation method thereof based on graft copolymer |
| CN108530659B (en) * | 2018-05-17 | 2021-08-27 | 苏州大学 | Polyphenylene oxide-polysiloxane photo-crosslinked film based on graft copolymer and preparation method thereof |
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|---|---|
| CN1167743C (en) | 2004-09-22 |
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