CN105219066B - A kind of polyurethane/nano hydrotalcite composite material with high-damping, UV absorption and toughness reinforcing performance and preparation method thereof - Google Patents
A kind of polyurethane/nano hydrotalcite composite material with high-damping, UV absorption and toughness reinforcing performance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polyurethane/nano hydrotalcite composite material and preparation method thereof, belong to polymer nanocomposites field.Its preparation technology can be briefly summarized as following steps：Dodecyl sodium sulfonate root intercalation is carried out to nano hydrotalcite presoma, the modification of silane coupler surface grafting, obtains the organic decoration hydrotalcite of favorable dispersibility；Synthesize the base polyurethane prepolymer for use as of specific isocyano-content；The organic hydrotalcite of different content is mixed with base polyurethane prepolymer for use as, adds the PPG, crosslinking agent, catalyst in-situ polymerization of specific metering；After reacting a period of time, by product casting film-forming in a template, polyurethane nano hydrotalcite composite material is obtained.Composite prepared by the present invention shows more preferable damping characteristic, toughness and ultraviolet absorption ability compared with common polyurethane material, and cost is cheap, technique is simple, high comprehensive performance, has broad application prospects.
Description
Technical field
The invention belongs to polymer nanocomposites field, in particular, provide it is a kind of have high-damping UV absorption and
The polyurethane nano hydrotalcite composite material and its preparation method of toughness reinforcing performance.
Background technology
In recent years, polymer nanocomposites are just constantly paid close attention to and studied by people.Polymer nanocomposites are
Refer to using polymer as organic phase, novel-section obtained from carrying out compound assembling with organic phase nano particle or inorganic phase nano particle
Material.Because polymer has machinability, plasticity and functional diversity, make nano composite material main carriers it
One.Polymer is the important branch of nanometer science and technology with inorganic nano combined, and prepares high-performance polymer material
One of important channel.
Polyurethane is a kind of widely used polymeric material, can be used for the neck such as coating, adhesive, elastomer, ink
Domain, as one of the synthetic material with development prospect greatly of the world six, it is developed rapidly in recent years in China.But its own is deposited
In some shortcomings, as intensity is not high, heat-resisting, poor performance etc., limits its and further apply.On the other hand, some researchers use
Epoxy resin, montmorillonite, natural products and with being modified the methods of plastic blend to it.In recent years, inorganic nano material
It is modified to turn into one of polyurethane-modified Main Means.The polyurethane inorganic nanometer synthesized by inorganic nano material modified shape is answered
Condensation material, can significantly improve mechanical property, the heat endurance of high polymer material, and assign some special performance, therefore
This means enjoys the concern of domestic and international investigation of materials person in recent years, and is constantly promoting the development of polyurethane industrial.
It is a kind of that layered bi-metal complex hydroxide, which is also known as hydrotalcite (Layered Double Hydroxide, LDH),
New multi-functional layered nano material, has a wide range of applications.Piece layer charge density is higher in itself for hydrotalcite, due on lamella
Hydroxyl make sheet surfaces that there is very strong polarity, cause the interaction of neatly rock layers and layer very strong, it is difficult in polymer matrix
Leafing in body.But due to hydrotalcite its with laminate metallic element is adjustable, interlayer ion is replaceable, with layer structure, green
A variety of advantages such as environmental protection make it have potential researching value on polymer based nanocomposites are prepared, just constantly by people
It is of interest.
The present invention is intimately associated uniform effective scattering problem of nano particle in current polymer nanocomposites, passes through
Dodecyl sodium sulfonate root intercalation nitrate anion hydrotalcite precursor, it is big, scattered that interlamellar spacing is made in silane coupler surface graft modification
Property good organic modified nano neatly hardcore, and using polyurethane nano composite material as point of penetration, design has been synthesized with poly- ammonia
Ester is matrix, and organic modified nano hydrotalcite is a kind of nano composite material of dispersed phase.Nanoparticle after due to modification
Size is small, compatibility is good, specific surface area is big, surface energy and surface tension increased dramatically with the decline of particle diameter, shows surface effect
Should, small-size effect etc., composite is possessed many new kink characteristics for being different from conventional material, such as more preferable mechanical property,
Higher damping characteristic, heat endurance and uvioresistant ability significantly improve.The present invention is applied to poly- for organic nano hydrotalcite
Urethane material opens new thinking.
The content of the invention
It is an object of the invention to provide a kind of preparation of the polyurethane nano hydrotalcite composite material with excellent properties
Method.The present invention is using the laminar nano hydrotalcite of dodecyl sodium sulfonate root intercalation silane coupler surface graft modification as one kind
New material is applied to the modification to polyurethane elastomer, uniformly and effectively disperses in polyurethane matrix for hydrotalcite, designs
Synthesis is significantly improved with high damping characteristic, high tenacity, heat endurance and uvioresistant ability, excellent combination property it is nano combined
Material provides new thinking and Feasibility Solution.
The technical scheme is that hydrotalcite precursor is carried out into organic modification, it is allowed in polyurethane matrix equal
It is even effectively scattered.Using the crosslinking invigoration effect of nano hydrotalcite and polyurethane matrix, by in-situ inserted/in-situ polymerization, molten
Agent volatilization casting film-forming, realizes the polyurethane nano composite material for preparing excellent combination property.Specific preparation process is as follows：
I. the preparation of organic decoration hydrotalcite
1) magnaliums nitrate anion hydrotalcite (MgAl-NO3- LDH) presoma preparation
A. 0.03~0.3mol magnesium nitrates (Mg (NO are weighed3)2·6H2O), 0.01~0.1mol aluminum nitrates (Al (NO3)3·
9H2O), the two mixing is dissolved in 100~300ml deionized waters to (deionized water leads to the boiled removal CO of nitrogen2, similarly hereinafter), note
For solution A；
B. configuration and 100~300ml of NaOH solution of 1.0~4.0 times of amounts of metal ion mole summation in step a, note
For solution B；
C. solution A and solution B are poured slowly into colloid mill simultaneously, colloid mill 2000~4000r/min of rotating speed, nucleation 1
After~5min, transferring the slurry into immediately in there-necked flask, be passed through nitrogen, heating water bath stirs 12~24h of crystallization at 70~95 DEG C,
Mechanical agitation rotating speed is 300~500r/min (similarly hereinafter)；
D. product is fully washed with deionized water and centrifuged 3~6 times respectively, to cleaning solution it is colourless in neutrality, 50
MgAl-NO is can obtain after 10~24h is dried in vacuo at~90 DEG C3- LDH presomas；
2) ion-exchanges prepare dodecyl sodium sulfonate root intercalated houghite (SD-LDH)
A. 1.0~4.0gMgAl-NO is weighed3- LDH is dissolved in 100~300ml deionized waters, is designated as solution C；
B. 0.01~0.1mol dodecyl sodium sulfates (SDS) are weighed to be dissolved in 100~300ml deionized waters, are designated as molten
Liquid D；
C. solution C and solution D are poured into there-necked flask, under nitrogen protection, at 70~90 DEG C heating water bath stirring 18~
24h；
D. product is fully washed with deionized water and centrifuged 3~6 times respectively, to cleaning solution it is colourless in neutrality, 50
SD-LDH is can obtain after 10~24h is dried in vacuo at~90 DEG C；
3) preparation of silane couplers surface modification intercalated houghite (APS-SD-LDH)
A. weigh 1.0~5.0gSD-LDH to be dissolved in 30~100ml ethanol solutions, stir 0.5~1.0h, it is to be formed
After slurries, add 3~10ml deionized waters, 5~10ml APTES (APS), continue stirring 5~
8h；
B. product is fully washed with absolute ethyl alcohol and centrifuged 3~6 times respectively, it is colourless to cleaning solution, 50~90 DEG C
The hydrotalcite of organic modification, i.e. APS-SD-LDH are can obtain after 10~24h of lower vacuum drying.
II. the synthesis of polyurethane prepolymer
A. by a certain amount of PPG (PPG-1000) with heating mantle heats to 100~110 DEG C, vacuumize stirring 1
~2h, completely dehydration, are designated as reactant A, mechanical agitation rotating speed is 200~400r/min (similarly hereinafter)；
B. A is cooled to 50~70 DEG C, adds a certain amount of toluene di-isocyanate(TDI) (TDI) or the isocyanide of diphenyl methane two
Acid esters (MDI), 80~90 DEG C are stirred and heated to, react 1.5~3h.Products therefrom is that isocyanate content is 3%~6%
TDI or MDI performed polymers.
III. the synthesis of polyurethane/nano hydrotalcite composite material
A. 8.0~12.0g performed polymers are weighed, is dissolved in 10~50ml anhydrous tetrahydro furans (THF), is heated in there-necked flask
0.5~1h is stirred, 50~70 DEG C of keeping temperature, leads to nitrogen protection, mechanical agitation rotating speed is 300~500r/min (similarly hereinafter), note
For reactant A；
B. 1%~5% APS-SD-LDH of different proportion is weighed, is scattered in the anhydrous THF of 10~30ml, in there-necked flask
Middle 0.5~1h of heating stirring, 30~50 DEG C of keeping temperature, lead to nitrogen protection, be designated as reactant B；
C. reactant B is transferred in reactant A, keeps temperature-resistant in A, after continuing 1~2h of stirring, add 2.0
~5.0gPPG-1000,0.2~0.3g trimethylolpropanes (TMP), keep the n (- NCO) of reaction system:N (- OH)=1~2；
D. stop reaction when the obvious retrogradation of question response system, and product is quickly transferred to ptfe surface ware
In, casting film-forming, obtain polyurethane/nano hydrotalcite composite material.
Present invention be characterized in that Nano filling is organic modification hydrotalcite, organic decoration hydrotalcite addition 1%
Any one in~10%.Described M2+For Mg2+、Ni2+、Co2+、Ca2+、Cu2+、Zn2+Any one of；Described M3+
For Al3+、Ga3+、In3+、Cr3+Any one of；Polyurethane prepolymer is toluene di-isocyanate(TDI) (TDI) or diphenylmethyl
Any one in alkane diisocyanate (MDI)；Any one in organic hydrotalcite addition 1%~10%.
The advantage of the invention is that：The nano lamellar water of dodecyl sodium sulfonate root intercalation silane coupler surface graft modification
Talc materials uniformly and effectively can be dispersed in polyurethane matrix, strong by being cross-linked with each other for laminar nano hydrotalcite and matrix
Change acts on, and changes the addition of neatly hardcore, the polyurethane nano composite material of excellent combination property has successfully been made, and
Neatly hardcore is green, cheap and easy to get.
Brief description of the drawings
Fig. 1 be under the conditions of specific embodiment of the invention example one obtained composite sample and pure polyurethane samples should
Stress-strain contrasts spectrogram, and abscissa is strain (%), and ordinate is intensity (MPa).
Fig. 2 is the composite sample obtained under the conditions of specific embodiment of the invention example two and the purple of pure polyurethane samples
Outer to absorb contrast spectrogram, abscissa is wavelength, unit:Nanometer；Ordinate is absorption intensity.
Embodiment
【Embodiment 1】
I. the preparation of organic decoration hydrotalcite
1).MgAl-NO3The preparation of-LDH presomas
A. 0.05molMg (NO are weighed3)2·6H2O、0.025molAl(NO3)3·9H2O, the two mixing is dissolved in 100ml
(deionized water leads to the boiled removal CO of nitrogen in deionized water2, similarly hereinafter), it is designated as solution A；
B. configuration and the NaOH solution 100ml of 2 times of amounts of metal ion mole summation in step a, are designated as solution B；
C. solution A and solution B are poured slowly into vertical colloid mill (JM-50 types, similarly hereinafter) simultaneously, colloid mill rotating speed
4000r/min, after being nucleated 3min, transfer the slurry into immediately in there-necked flask, be passed through nitrogen, heating water bath stirs crystallization at 90 DEG C
12h, mechanical agitation rotating speed are 400r/min (similarly hereinafter)；
D. product is fully washed with deionized water and centrifuged 4 times respectively, it is colourless in neutrality to cleaning solution；At 60 DEG C
Vacuum drying can obtain MgAl-NO after 24 hours3- LDH presomas；
2) .SD-LDH preparation
A. 3.0gMgAl-NO is weighed3- LDH is dissolved in 100ml deionized waters, is designated as solution C；
B. 0.02mol SDS are weighed to be dissolved in 100ml deionized waters, are designated as solution D；
C. solution C and solution D are poured into there-necked flask, under nitrogen protection, heating water bath stirs 18h at 90 DEG C；
D. product is fully washed with deionized water and centrifuged 5 times respectively, it is colourless in neutrality to cleaning solution；At 60 DEG C
Vacuum drying can obtain SD-LDH after 24 hours；
3) .APS-SD-LDH preparation
A. weigh 2.0gSD-LDH to be dissolved in 50ml ethanol solutions, stirring 0.5h, after slurries to be formed, add 5ml
Deionized water, 5mlAPS, continue to stir 5h；
B. product is fully washed with absolute ethyl alcohol and centrifuged 5 times respectively, it is colourless to cleaning solution；Vacuum is done at 60 DEG C
Organically-modified hydrotalcite APS-SD-LDH is can obtain after dry 24 hours.
II. the synthesis of polyurethane prepolymer
A. by a certain amount of PPG-1000 heating mantle heats to 110 DEG C, stirring 2h, completely dehydration are vacuumized, is designated as anti-
Answer thing A；
B. A is cooled to 60 DEG C, adds a certain amount of TDI, be stirred and heated to 85 DEG C, react 2h, products therefrom is isocyanide
Acid and esters content is 5.85% TDI performed polymers.
III. the synthesis of polyurethane/nano hydrotalcite composite material
A. 10.0g performed polymers are weighed, are dissolved in the anhydrous THF of 20ml, the heating stirring 1h in there-necked flask, keeping temperature 60
DEG C, lead to nitrogen protection, be designated as reactant A；
B. 2% (0.2g) APS-SD-LDH is weighed, is scattered in the anhydrous THF of 20ml, the heating stirring 1h in there-necked flask,
60 DEG C of keeping temperature, lead to nitrogen protection, be designated as reactant B；
C. reactant B is transferred in reactant A, keeps temperature-resistant in A, continued after stirring 2h, add 2.2g
PPG-1000,0.25g trimethylolpropane (TMP), 5 drop phenylmercuric acetate catalyst, keep the n (- NCO) of reaction system:n(-
OH)=1.3；
D. stop reaction when the obvious retrogradation of question response system, and product is quickly transferred to ptfe surface ware
In, casting film-forming, obtain polyurethane/nano hydrotalcite composite material.
【Embodiment 2】
I. the preparation of organic decoration hydrotalcite
1).MgAl-NO3The preparation of-LDH presomas
A. 0.05molMg (NO are weighed3)2·6H2O、0.025molAl(NO3)3·9H2O, the two mixing is dissolved in 100ml
(deionized water leads to the boiled removal CO of nitrogen in deionized water2, similarly hereinafter), it is designated as solution A；
B. configuration and the NaOH solution 100ml of 2 times of amounts of metal ion mole summation in step a, are designated as solution B；
C. solution A and solution B are poured slowly into vertical colloid mill (JM-50 types, similarly hereinafter) simultaneously, colloid mill rotating speed
4000r/min, after being nucleated 3min, transfer the slurry into immediately in there-necked flask, be passed through nitrogen, heating water bath stirs crystallization at 90 DEG C
12h, mechanical agitation rotating speed are 400r/min (similarly hereinafter)；
D. product is fully washed with deionized water and centrifuged 4 times respectively, it is colourless in neutrality to cleaning solution；At 60 DEG C
Vacuum drying can obtain MgAl-NO after 24 hours3- LDH presomas；
2) .SD-LDH preparation
A. 3.0gMgAl-NO is weighed3- LDH is dissolved in 100ml deionized waters, is designated as solution C；
B. 0.02mol SDS are weighed to be dissolved in 100ml deionized waters, are designated as solution D；
C. solution C and solution D are poured into there-necked flask, under nitrogen protection, heating water bath stirs 18h at 90 DEG C；
D. product is fully washed with deionized water and centrifuged 5 times respectively, it is colourless in neutrality to cleaning solution；At 60 DEG C
Vacuum drying can obtain SD-LDH after 24 hours；
3) .APS-SD-LDH preparation
A. weigh 2.0gSD-LDH to be dissolved in 50ml ethanol solutions, stirring 0.5h, after slurries to be formed, add 5ml
Deionized water, 5mlAPS, continue to stir 5h；
B. product is fully washed with absolute ethyl alcohol and centrifuged 5 times respectively, it is colourless to cleaning solution；Vacuum is done at 60 DEG C
Organically-modified hydrotalcite APS-SD-LDH is can obtain after dry 24 hours.
II. the synthesis of polyurethane prepolymer
A. by a certain amount of PPG-1000 heating mantle heats to 110 DEG C, stirring 2h, completely dehydration are vacuumized, is designated as anti-
Answer thing A；
B. A is cooled to 60 DEG C, adds a certain amount of TDI, be stirred and heated to 85 DEG C, react 2h, products therefrom is isocyanide
Acid and esters content is 5.85% TDI performed polymers.
III. the synthesis of polyurethane/nano hydrotalcite composite material
A. 10.0g performed polymers are weighed, are dissolved in the anhydrous THF of 20ml, the heating stirring 1h in there-necked flask, keeping temperature 60
DEG C, lead to nitrogen protection, be designated as reactant A；
B. 3% (0.3g) APS-SD-LDH is weighed, is scattered in the anhydrous THF of 20ml, the heating stirring 1h in there-necked flask,
60 DEG C of keeping temperature, lead to nitrogen protection, be designated as reactant B；
C. reactant B is transferred in reactant A, keeps temperature-resistant in A, continued after stirring 2h, add 2.2g
PPG-1000,0.25g TMP, 5 drop phenylmercuric acetate catalyst, keep the n (- NCO) of reaction system:N (- OH)=1.3；
D. stop reaction when the obvious retrogradation of question response system, and product is quickly transferred to ptfe surface ware
In, casting film-forming, obtain polyurethane/nano hydrotalcite composite material.
Claims (1)
1. a kind of preparation method of the polyurethane/nano hydrotalcite composite material with high-damping, UV absorption and toughness reinforcing performance,
Characterized in that, composite compares pure polyurethane material, when hydrotalcite filer content is 2%, its UV absorption intensity carries
It is high by 33%；When hydrotalcite filer content is 3%, its elongation at break improves 325%；When hydrotalcite filer content is
When 2%, its damping factor maximum improves 8.3%, and damping temperature domain becomes big；
The specific preparation process of composite is as follows：
I. the preparation of organic decoration hydrotalcite
1) preparation of magnaliums nitrate anion hydrotalcite precursor
A. 0.03~0.3mol magnesium nitrates, 0.01~0.1mol aluminum nitrates are weighed, by the two mix be dissolved in 100~300ml go from
In sub- water, deionized water has led to nitrogen and has removed CO2, it is designated as solution A；
B. 100~300mL of NaOH solution with 1.0~4.0 times of amounts of metal ion mole summation in step a is prepared, is designated as molten
Liquid B；
C. solution A and solution B are poured slowly into vertical colloid mill simultaneously, colloid mill 2000~4000r/min of rotating speed, nucleation 1
After~5min, transferring the slurry into immediately in there-necked flask, be passed through nitrogen, heating water bath stirs 12~24h of crystallization at 70~95 DEG C,
Mechanical agitation rotating speed is 300~500r/min；
D. product is fully washed with deionized water and centrifuged 3~6 times respectively, to cleaning solution it is colourless in neutrality, 50~90
MgAl-NO is obtained after 10~24h is dried in vacuo at DEG C3- LDH presomas；
2) ion-exchanges prepare dodecyl sodium sulfonate root intercalated houghite
A. 1.0~4.0g MgAl-NO is weighed3- LDH is dissolved in 100~300mL deionized waters, is designated as solution C；
B. 0.01~0.1mol dodecyl sodium sulfates are weighed to be dissolved in 100~300mL deionized waters, are designated as solution D；
C. solution C and solution D are poured into there-necked flask, under nitrogen protection, heating water bath stirs 18~24h at 70~90 DEG C；
D. product is fully washed with deionized water and centrifuged 3~6 times respectively, to cleaning solution it is colourless in neutrality, 50~90
SD-LDH is obtained after 10~24h is dried in vacuo at DEG C；
3) preparation of silane couplers surface modification intercalated houghite
A. the SD-LDH for weighing 1.0~5.0g is dissolved in 30~100mL ethanol solutions, stirs 0.5~1.0h, slurry to be formed
After liquid, 3~10mL deionized waters, 5~10mL APTES are added, continues 5~8h of stirring；
B. product is fully washed with absolute ethyl alcohol and centrifuged 3~6 times respectively, it is colourless to cleaning solution, it is true at 50~90 DEG C
Sky obtains the hydrotalcite of organic modification, i.e. APS-SD-LDH after drying 10~24h；
II. the synthesis of polyurethane prepolymer
A. PPG heating mantle heats are vacuumized into 1~2h of stirring to 100~110 DEG C, completely dehydration, is designated as reacting
Thing A, mechanical agitation rotating speed are 200~400r/min；
B. A is cooled to 50~70 DEG C, adds toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate, be stirred and heated to 80
~90 DEG C, 1.5~3h is reacted, products therefrom is the toluene di-isocyanate(TDI) or diphenylmethyl that isocyanate content is 3%~6%
Alkane diisocyanate prepolymer body；
III. the synthesis of polyurethane/nano hydrotalcite composite material
A. 8.0~12.0g performed polymers are weighed, are dissolved in 10~50mL anhydrous tetrahydro furans, in there-necked flask heating stirring 0.5~
1h, 50~70 DEG C of keeping temperature, lead to nitrogen protection, mechanical agitation rotating speed is 300~500r/min, is designated as reactant A；
B. 1%~5% APS-SD-LDH of different proportion is weighed, is scattered in the anhydrous THF of 10~30mL, is added in there-necked flask
0.5~1h of thermal agitation, 30~50 DEG C of keeping temperature, lead to nitrogen protection, be designated as reactant B；
C. reactant B is transferred in reactant A, keeps temperature-resistant in A, after continuing 1~2h of stirring, addition 2.0~
5.0g PPGs, 0.2~0.3g trimethylolpropanes, keep the n (- NCO) of reaction system:N (- OH)=1~2；
D. stop reaction when the obvious retrogradation of question response system, and quickly product be transferred in ptfe surface ware,
Casting film-forming, obtain polyurethane/nano hydrotalcite composite material.
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| CN106750088A (en) * | 2016-12-26 | 2017-05-31 | 合肥富铭密封材料有限公司 | A kind of preparation method of flame resistance polyurethane elastomer |
| CN106674598A (en) * | 2017-01-05 | 2017-05-17 | 广州光通电子科技有限公司 | Preparation method for efficient modified layered double-hydroxide flame retardant additive |
| CN106916280A (en) * | 2017-04-14 | 2017-07-04 | 陕西科技大学 | No-solvent type polyurethane nano hydrotalcite composite membrane and preparation method thereof |
| CN107216791A (en) * | 2017-06-28 | 2017-09-29 | 常州万博金属构件厂 | A kind of fabric flame-retardant coatings glue and preparation method thereof |
| CN108079798B (en) * | 2017-12-15 | 2021-04-13 | 北京林业大学 | Preparation method of super-hydrophilic organic membrane based on nano hydrotalcite-like compound |
| CN110894277B (en) * | 2019-11-15 | 2021-02-19 | 华南理工大学 | High-temperature-resistant wide-temperature-range high-damping polyurethane elastomer material and preparation method thereof |
| CN114057977B (en) * | 2021-12-14 | 2023-02-24 | 安徽誉林新材料科技有限公司 | Low-heat-rise high-strength polyurethane tire for forklift |
| CN114276516B (en) * | 2022-01-14 | 2022-11-18 | 浙江佳人新材料有限公司 | Method for preparing hard polyurethane foam by using byproducts of waste textile chemical method regeneration process |
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| CN1376748A (en) * | 2002-04-09 | 2002-10-30 | 孔克健 | Environment protection type polyurethane elastomer/laminated nano composition and its preparing process |
| CN1376749A (en) * | 2002-04-09 | 2002-10-30 | 孔克健 | Polyurethane elastomer/laminated nano composition for stadium and its preparing process |
| CN101560271A (en) * | 2009-05-25 | 2009-10-21 | 浙江工业大学 | Method for preparing polymer/houghite nano composite material |
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| CN1376748A (en) * | 2002-04-09 | 2002-10-30 | 孔克健 | Environment protection type polyurethane elastomer/laminated nano composition and its preparing process |
| CN1376749A (en) * | 2002-04-09 | 2002-10-30 | 孔克健 | Polyurethane elastomer/laminated nano composition for stadium and its preparing process |
| CN101560271A (en) * | 2009-05-25 | 2009-10-21 | 浙江工业大学 | Method for preparing polymer/houghite nano composite material |
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