CN101928477A - Modified stratified material and unsaturated polyester nano composite material - Google Patents
Modified stratified material and unsaturated polyester nano composite material Download PDFInfo
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- CN101928477A CN101928477A CN2009101461875A CN200910146187A CN101928477A CN 101928477 A CN101928477 A CN 101928477A CN 2009101461875 A CN2009101461875 A CN 2009101461875A CN 200910146187 A CN200910146187 A CN 200910146187A CN 101928477 A CN101928477 A CN 101928477A
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Abstract
The embodiment of the invention provides a modified stratified material comprising a stratified inorganic material, wherein the sandwich layer of the stratified inorganic material contains an organic modifier. The organic modifier comprises a compound shown as a formula (I) or (II), wherein M represents metal, R1 represents a long carbon chain, R2 represents a long carbon chain, and X- represents an anion. The embodiment of the invention also relates to a high-performance unsaturated polyester nano composite material comprising the modified stratified material and a high-polymer substrate containing unsaturated polyester resins.
Description
Technical field
The present invention relates to modified stratified material, and be particularly related to the nano composite material of modified stratified material/unsaturated polyester resin.
Background technology
Unsaturated polyester resin is suitable for for example forming hard plastic articles by the heat cross-linking that adds thermal initiation because of having unsaturated functional group, and its transparency, weathering resistance, and color fastness aspect quite excellent, so it is widely used in material of construction, electronic material, sanitary bath equipment, and sheet material etc.
Unsaturated polyester resin follows bigger contraction, its volumetric shrinkage can reach more than 10% in sclerosis often, easily causes unsaturated polyester resin material gross distortion, breaks or produce phenomenons such as screw thread seal.For example, (Fiber Reinforced Plastics, FRP) plate surface easily has phenomenons such as screw thread seal to utilize the common fibre reinforced plastics of forming of unsaturated polyester resin material and glass fibre.For improving the excessive problem of unsaturated polyester resin shrinking percentage, can be to wherein adding various shrinking agents or low profile agent.Shrinking agent commonly used has polystyrene (PS), polymethylmethacrylate (PMMA), vinylbenzene etc.Yet the interpolation of shrinking agent often causes the physical strength of unsaturated polyester resin to reduce, and limits its application thus.
Therefore, be badly in need of the material in polyester resin that volumetric shrinkage is lower and have enough physical strengths in this area.
Summary of the invention
Embodiment of the present invention provides a kind of modified stratified material, and it comprises that intercalation (intercalate) has the layered inorganic material of organic modifiers, and this organic modifiers comprises
Wherein M represents metal, R
1The long carbochain of expression, R
2The long carbochain of expression, and X
-The expression negatively charged ion.
Another embodiment of the present invention provides a kind of unsaturated polyester nano composite material, it comprises polymer matrix and aforesaid modified stratified material, this polymer matrix comprises unsaturated polyester resin, and wherein this modified stratified material is scattered in this polymer matrix and peels off (exfoliated) at least in part.
Description of drawings
Fig. 1 shows the TEM photo of the unsaturated polyester nano composite material of one embodiment of the invention.
Embodiment
Modified stratified material of the present invention obtains by with organic modifiers the layered inorganic material being carried out intercalation modifying.Unsaturated polyester nano composite material of the present invention comprises polymer matrix, and is dispersed with above-mentioned modified stratified material in the polymer matrix, and modified stratified material is peeled off at least in part.Polymer matrix comprises unsaturated polyester resin, and when wherein being dispersed with modified stratified material of the present invention, its structural stability can get a promotion.
General unsaturated polyester resin has very big volumetric shrinkage after crosslinked, this will cause tremendous influence to its character.Embodiment of the present invention is disperseed by importing the modified stratified material of peeling off at least in part and make it in unsaturated polyester resin, by these dispersive modified stratified materials, can constitute three-dimensional steric barrier in unsaturated polyester resin, the unsaturated polyester nano composite material that unsaturated polyester resin and modified stratified material are formed has dimensional stability preferably.
Be suitable for layered inorganic material of the present invention and can be natural clay or synthetic inorganic lamellar material, the for example combination of smectic clays (smectite clay), vermiculite, halloysite (halloysite), sericite, mica, zirconium phosphate class derivative compound, the two oxyhydroxides (LDH, layered double hydroxides) of stratiform or aforementioned substances.Wherein, smectic clays comprises the combination of for example polynite, bentonite (saponite), beidellite (beidellite), canbyite (nontronite), lithium soap soil (hectorite) or aforementioned substances.In one embodiment, the layered inorganic material is cationic exchange type (inorganic lamellar material that promptly has the interlayer cation exchange capacity), and its cationic exchange equivalent can be about 50～250meq/100g.In addition, also can use other to have the normal layered inorganic material of higher or lower cationic exchange, for example its cationic exchange equivalent can be about 250～500meq/100g or is about 10～50meq/100g.
Be fit to that organic modifiers needs of the present invention can carry out ion-exchange with the layered inorganic material and intercalation among the layered inorganic material.In one embodiment, the organic modifiers of Shi Heing has structural formula as follows:
Wherein, M represents metal, basic metal such as lithium, sodium, potassium for example, and R
1The long carbochain of expression.The long carbochain that is fit to comprises saturated long carbochain or unsaturated long carbochain, and it contains carbon number can for example be 10 to 30, but is not limited thereto.In addition, long carbochain also can comprise one or more side chains, can comprise saturated carbon chains, unsaturated carbon chains and/or other functional group in the side chain.
In another embodiment, the organic modifiers of Shi Heing has structural formula as follows:
Wherein, X
-The expression negatively charged ion, halide-ionss such as chlorion, bromide anion, iodide ion for example, and R
2The long carbochain of expression.The long carbochain that is fit to comprises saturated long carbochain or unsaturated long carbochain, and it contains carbon number can for example be 10 to 30, but is not limited thereto.In addition, long carbochain also can comprise one or more side chains, can comprise saturated carbon chains, unsaturated carbon chains and/or other functional group in the side chain.
Modified stratified material of the present invention can form in the following manner.At first, place the deionized water swelling about more than 4 hours layered inorganic material (for example laminated clay), this step helps organic modifiers to enter among the layered inorganic material.Then, can add an amount of organic modifiers, organic modifiers is diffused among the layered inorganic material, thereby and carry out the ion-exchange bond among the layered inorganic material with the layered inorganic material that is contacted.In a kind of modified stratified material of embodiment, the shared weight percent of organic modifiers is that about 5 weight % are to about 30 weight %.In the modified stratified material of another embodiment, the shared weight percent of organic modifiers is that about 10 weight % are to about 20 weight %.
The layered inorganic material at intercalation behind the organic modifiers, its interlayer spacing can be strutted, its interlayer spacing is for example greater than approximately
The modified stratified material that the interlayer spacing struts can allow high molecular monomer be easy to enter interlayer, thereby form modified stratified material-polymer composite jointly, and the bigger modified layered clay of interlayer spacing can peel off more easily and delamination is scattered in the polymer matrix in polymer matrix.
The unsaturated polyester nano composite material of embodiment of the present invention comprises polymer matrix and the above-mentioned modified stratified material that contains unsaturated polyester resin, and modified stratified material is scattered in the polymer matrix and peels off at least in part.In a kind of unsaturated polyester nano composite material of embodiment, the shared weight percent of modified stratified material is roughly about 0.1 weight % to about 7 weight %.In the unsaturated polyester nano composite material of another embodiment, the shared weight percent of modified stratified material is roughly about 1 weight % to about 5 weight %.In the unsaturated polyester nano composite material of another embodiment, the shared weight percent of modified stratified material is about 3 weight %.It should be noted that in the unsaturated polyester nano composite material of embodiment of the present invention, the content of modified stratified material can according to circumstances be adjusted, and is not limited to aforesaid content range.
The generation type of the unsaturated polyester nano composite material of embodiment of the present invention is for example can to mix by the monomer that modified stratified material is required with forming polymer matrix, makes monomer polymerization reaction take place (for example by heating up or the interpolation catalyzer) in the interlayer spacing of modified stratified material of polymer matrix.When monomer forms polymer matrix via polyreaction, help to make modified stratified material to peel off and be scattered in the polymer matrix.Unsaturated polyester resin synthetic can be for example by various unsaturated dibasic acids, various monounsaturated dicarboxylic acid, and various dibasic alcohol etc. carry out condensation reaction and realize.The unsaturated dibasic acid that is fit to for example is MALEIC ANHYDRIDE (MA, or title maleic anhydride) and/or FUMARIC ACID TECH GRADE (FA) etc., but is not limited thereto.The monounsaturated dicarboxylic acid that is fit to for example is Tetra hydro Phthalic anhydride (PA), m-phthalic acid (IPA) and/or terephthalic acid (TPA) etc., but is not limited thereto.The dibasic alcohol that is fit to for example is 1, and (propylene glycol PG), glycol ether (DEG), neopentyl glycol (NPG) and/or ethylene glycol (EG) etc., but is not limited thereto the 2-propylene glycol.
For example, in one embodiment, aforementioned modified stratified material is dissolved in the solvent to form the solution of modified stratified material.The solvent that is fit to for example is glycolic solvents such as propylene glycol, but is not limited thereto.Then, the monomer of unsaturated polyester resin is added in the solution of modified stratified material and dispersed with stirring.The monomer of the unsaturated polyester resin that is fit to for example can be the mixture of maleic anhydride and Tetra hydro Phthalic anhydride.Yet, it will be understood by those skilled in the art that the compound that is suitable for forming unsaturated polyester resin is not limited to above cited example, can adopt various other compounds to come polymerization to generate unsaturated polyester resin according to application scenarios.
The polyester unsaturated monomer of gained and the mixing solutions of modified stratified material are after the suitable thermal treatment of process, the monomer of unsaturated polyester resin just can form unsaturated polyester resin matrix by polyreaction, and makes modified stratified material peel off and be scattered in the unsaturated polyester resin matrix.Wherein, thermal treatment can adopt the mode that increases thermostat temperature one by one to carry out condensation reaction for for example hardening about 15 hours to about 20 hours between about 100 ℃ to 200 ℃.
On the other hand, unsaturated polyester nano composite material of the present invention also can by modified stratified material directly with mixing the forming of polymer matrix of containing unsaturated polyester resin.For example can adopt melt blending or solution blending.Generally speaking, melt blending can carry out in closed system, for example can utilize surging mixing facilities such as single screw rod or multiple screw extruder, Banbury Banbury mixer, twin-screw mixer machine, single screw mixing machine, ten thousand horsepowers of machines, continuous mixer, Kneader kneader, under enough high temperature, both be carried out melting mixing and get final product.The temperature of melt blending is about 150 ℃～250 ℃.Solution blending is modified stratified material to be added be dissolved with in the organic solvent of polymer matrix, and high-speed stirring is even, and the mixture of gained can obtain unsaturated polyester nano composite material after removing organic solvent.For example, it is mixing directly to place mixing facilities to carry out polymeric unsaturated polyester resin matrix and modified stratified material, and because mixing facilities is surging mixing, modified stratified material also can be peeled off and be scattered in the polymer matrix that includes unsaturated polyester resin at least in part.
According to the made unsaturated polyester nano composite material of aforesaid method can injection moulding, modes such as extrusion molding, compression moulding or priming by vacuum directly make various moulding product, or before molding or perfusion earlier with other polymkeric substance or compound blend.
The unsaturated polyester nano composite material of embodiment of the present invention is owing to comprise the modified stratified material that is scattered in the polymer matrix and peels off at least in part, thereby can make the structure of polymer matrix keep integrity, and make the difficult contraction of polymer matrix or produce screw thread seal phenomenon on the surface, effectively promote its mechanical properties.In addition, the modified stratified material of peeling off at least in part can help to block thermal source, further improves the flame-retardant nature of matrix material.The unsaturated polyester nano composite material of embodiment of the present invention is particularly suitable for being applied to resin peculiar to vessel or various sanitary bath equipment.For example, in one embodiment, unsaturated polyester nano composite material can be mixed with glass fibre and form fibre reinforced plastics (FRP) jointly, it can be used as bunker board.Because the importing of modified stratified material can make the polymer matrix that includes unsaturated polyester resin be difficult for shrinking, and these mechanical performance of products are significantly promoted.In addition, because the bunker board of being produced with unsaturated polyester nano composite material of the present invention or the surface of sanitary bath equipment be flat-satin and rare screw thread seal phenomenon takes place very, thereby can significantly save follow-up flat-satin manufacturing processed, can significantly save manufacturing cost, and the better product of obtained performance.Yet it should be noted that above-mentioned application only is the certain applications example of matrix material of the present invention, its range of application is not limited to above-mentioned specific examples.In addition, modified stratified material of the present invention also is not limited to be applied to comprise in the polymer matrix of unsaturated polyester resin.In other embodiments, modified stratified material of the present invention can import in other the macromolecular material system.In another embodiment, modified stratified material of the present invention can be applied to separately in various other systems, and is not limited to import in the polymer matrix.
In addition, in the matrix material that above-mentioned system is finished, also can add other composition, as malleableize agent, stiffening agent, fireproofing agent, compatilizer, organic-inorganic weighting agent, UV absorption agent, photostabilizer, static inhibitor, softening agent, lubrication prescription or antioxidant etc., this decides according to needed application.
Below enumerate several embodiment to further specify embodiments of the present invention.
Embodiment 1
Form modified stratified material
At first, will be more than 4 hours as swelling in the polynite adding deionized water of layered inorganic material.Then, thus adding an amount of organic modifiers makes it to carry out the ion-exchange intercalation to polynite with polynite.The organic modifiers that is adopted among the embodiment 1 has structural formula as follows:
Then, with deionized water to mixed solution clean repeatedly centrifugal after, with it drying for standby.
The modified stratified material of embodiment 1 gained carried out the XRD test and compare with the XRD figure spectrum of the polynite of non-modified, and the interplanar spacing of modified stratified material is by originally as can be known
Strut to
Show the successful intercalation of organic modifiers to polynite, and the interlayer interplanar spacing is strutted.
Embodiment 2
Form modified stratified material
The generation type of the modified stratified material of embodiment 2 and embodiment 1 are roughly the same.The difference part is that embodiment 2 adopts another kind of organic modifiers, and its structural formula is as follows:
The modified stratified material of embodiment 2 gained carried out the XRD test and compare with the XRD figure spectrum of the polynite of non-modified, and the interplanar spacing of modified stratified material is by originally as can be known
Strut to
Show the successful intercalation of organic modifiers to polynite, and the interlayer interplanar spacing is strutted.
Embodiment 3
Form unsaturated polyester nano composite material
Utilize mechanical stirrer that 197.5 gram propylene glycol are being mixed more than 12 hours under 80 ℃ with the modified stratified material of embodiment 1 gained.
Then, 92.5 gram maleic anhydrides and 210 gram Tetra hydro Phthalic anhydrides are put into polymerization reaction trough, and it is heated with the propylene glycol/modified stratified material solution that is pre-mixed.Temperature of reaction and time are as follows:
| Temperature | 120～140℃ | →200℃ | 200℃ | Cooling |
| Time | 6 hours | 4 hours | 6 hours |
After reaction is finished, cool off dilution.When temperature drops to 80 ℃, add quinhydrones and vinylbenzene dilutes and make its viscosity controller below 300cps, after stirring 6 hours, pour out.
The addition of the modified stratified material by control embodiment 1 gained, the weight percent that the modified stratified material in the unsaturated polyester nano composite material of may command embodiment 3 is shared.In embodiment 3, form four kinds of test pieces that the modified stratified material weight ratio is respectively 1 weight %, 3 weight %, 5 weight %, reaches 7 weight % altogether, they are carried out various performance tests together with the unsaturated polyester resin comparison test piece of not adding any modified stratified material, and wherein the preparation of various test pieces is to adopt the priming by vacuum method.
Embodiment 4
Form unsaturated polyester nano composite material
The generation type of the unsaturated polyester nano composite material of embodiment 4 and embodiment 3 are roughly the same.The difference part is that embodiment 4 changes the modified stratified material that adopts gained among the embodiment 2 into.In the unsaturated polyester nano composite material of embodiment 4, the shared weight percent of modified stratified material is 3 weight %.
In addition, the unsaturated polyester nano composite material of the embodiment of the invention is can be further mixing cured and form fibre reinforced plastics (FRP) sheet material jointly with the glass fibre lamination.With sheet glass is mould, and the glass fibre lamination is set thereon, then the unsaturated polyester nano composite material among the embodiment 3,4 is poured in the mould, thereby solidify to form fibre reinforced plastics (FRP) sheet material jointly with the glass fibre lamination with the priming by vacuum method.
XRD test is carried out in the test piece of embodiment 3,4 gained, can be found that the diffraction peak that originally belongs to modified stratified material all disappears, this shows modified stratified material delaminationization in polymer matrix.Fig. 1 shows the TEM photo of the unsaturated polyester nano composite material of the modified stratified material with 3 weight % among the embodiment 3, and its enlargement ratio is 60,000 times.Can find out modified stratified material delaminationization and being scattered in wherein in polymer matrix by the TEM photo of Fig. 1.
Table 1 shows unsaturated polyester nano composite material, and the volumetric shrinkage of comparative example test piece (promptly not adding the unsaturated polyester resin of modified stratified material) of unsaturated polyester nano composite material, the embodiment 4 of embodiment 3.Wherein, the measurement of volumetric shrinkage adopts Archimedes's method to carry out.Table 1 also shows with the volumetric shrinkage after these test pieces of UV light source irradiation.
Table 1
As shown in table 1, each embodiment compares with comparative example, and the volumetric shrinkage of each embodiment is all less than comparative example, thereby can improve unsaturated polyester resin because of the excessive problem that causes of volumetric shrinkage.In addition, even through the UV light source irradiation, volumetric shrinkage is still roughly constant, and this unsaturated polyester nano composite material that shows the embodiment of the invention can anti-solar radiation.In the above-described embodiments, the unsaturated polyester nano composite material with 3 weight % modified stratified materials of embodiment 3 has low especially volumetric shrinkage (5.65%), compare with comparative example (13.4%), its volumetric shrinkage has reduced about 7.75%, reduce volumetric shrinkage significantly, had outstanding especially effect.In addition, the unsaturated polyester nano composite material with 3 weight % modified stratified materials of embodiment 4 has lower volumetric shrinkage (3.36%), compare with comparative example (13.4%), its volumetric shrinkage has reduced about 10.04%, reduce volumetric shrinkage significantly, had outstanding especially effect.The unsaturated polyester nano composite material of the foregoing description is compared with the polymer matrix that does not add modified stratified material, and volumetric shrinkage reduces about 2% to about 11%.
FRP test piece test:
Table 2 shows the surfaceness that reaches prepared under the same conditions Comparative Example F RP test piece with the unsaturated polyester nano composite material of embodiment 3 and the FRP test piece of glass fibre lamination institute common formation.Wherein, the modified stratified material of the embodiment of the invention is not added in Comparative Example F RP test piece, and in addition, it is all identical to control other formation condition.Wherein, the measurement of surfaceness adopts surface roughness analysis instrument (surface analyzer) to carry out.Wherein, each numerical value is the mean value of 3 tests.
Table 2
| Comparative Example F RP | The FRP of embodiment 3 (3 weight %) | |
| Ra(μm) | 1.38 | 0.69 |
| Rmax(μm) | 9.01 | 3.60 |
Wherein, Ra is a mean roughness, and it is a center line average roughness; Rmax is a maximum height difference, i.e. difference of altitude between vertex and the lower-most point.As shown in table 2, the unsaturated polyester nano composite material of the embodiment of the invention is obviously smooth and smooth than comparative example FRP test piece with the surface that the glass fibre lamination forms the FRP test piece jointly, thereby can solve the problem that screw thread seal phenomenon easily takes place in the conventional FRP test piece.The FRP test piece of the foregoing description is compared with the Comparative Example F RP test piece of not adding modified stratified material, and mean roughness reduces about 0.7 μ m; Maximum height difference reduces about 5 μ m.
In addition, further with the FRP test piece and the Comparative Example F RP test piece of the fluorescent lamp irradiation embodiment of the invention, can find the reflected image of fluorescent lamp on the surface of the FRP of embodiment of the invention test piece.The fluorescent lamp reflectivity Comparative Example F RP test piece of the formed FRP test piece of the unsaturated polyester nano composite material of the embodiment of the invention is clear many, and the surface of the FRP test piece of the demonstration embodiment of the invention is obviously smooth and smooth than comparative example FRP test piece.
Table 3 shows the formed FRP test piece of unsaturated polyester nano composite material of embodiment 3 and the tension test test result of not adding the Comparative Example F RP test piece of modified stratified material.Wherein, each numerical value is the mean value of 10 tests (carrying out 10 tests with 10 roughly the same test pieces of size).
Table 3
| Comparative Example F RP | The FRP of embodiment 3 (3 weight %) | |
| Maximum loading (N) | 5434.128 | 5657.045 |
| Intensity (N/mm 2) | 291.229 | 325.454 |
As shown in table 3, the unsaturated polyester nano composite material of the embodiment of the invention and glass fibre lamination the common FRP test piece that forms compare with the Comparative Example F RP test piece of not adding modified stratified material, can bear bigger loading, and have higher intensity.The formed FRP test piece of the unsaturated polyester nano composite material of the foregoing description is compared with Comparative Example F RP test piece, and its tensile strength increases about 34N/mm
2
The flame retardant properties test:
Table 4 shows the unsaturated polyester nano composite material of embodiment 3 and the flame retardant properties test result of comparative example test piece.
Table 4
As shown in table 4, to compare with comparative example, the unsaturated polyester nano composite material of the embodiment of the invention has lower evenly heat release rate and total heat release, thereby can significantly promote the flame retardant properties of unsaturated polyester resin.The unsaturated polyester nano composite material of the foregoing description is compared with the polymer matrix that does not add modified stratified material, and its evenly heat release rate reduces about 90kW/m
2To about 410kW/m
2
In sum, the embodiment of the invention is by forming modified stratified material with the organic modifiers intercalation to the layered inorganic material.The modified stratified material of the embodiment of the invention can for example import in the polymer matrix that contains unsaturated polyester resin, and delaminationization and dispersion therein.Formed unsaturated polyester nano composite material is compared with the unsaturated polyester resin of the modified stratified material that does not import the embodiment of the invention, has significantly the mechanical property of the volumetric shrinkage that reduces, lifting, better surface flatness, and better flame retardant resistance.Particularly, the unsaturated polyester nano composite material of the embodiment of the invention can solve the screw thread seal problem that those skilled in the art are met with for a long time.
Though the present invention by some preferred implementations openly as above, yet it is not in order to restriction the present invention.The person of ordinary skill in the field can change arbitrarily and retouching, so protection scope of the present invention should be as the criterion with defined in the appended claims under the situation that does not break away from the spirit and scope of the present invention.
Claims (14)
1. modified stratified material comprises:
The layered inorganic material, its intercalation has organic modifiers, and this organic modifiers comprises
Wherein:
M represents metal;
R
1The long carbochain of expression;
R
2The long carbochain of expression; And
X
-The expression negatively charged ion.
2. modified stratified material as claimed in claim 1, wherein this organic modifiers comprises:
3. modified stratified material as claimed in claim 1, wherein this organic modifiers comprises:
4. modified stratified material as claimed in claim 1, wherein this layered inorganic material comprises natural clay or synthetic inorganic lamellar material.
5. modified stratified material as claimed in claim 1, wherein this layered inorganic material comprises the combination of smectic clays, vermiculite, halloysite, sericite, mica, zirconium phosphate class derivative compound, the two oxyhydroxides of stratiform or aforementioned substances.
6. modified stratified material as claimed in claim 5, wherein this smectic clays comprises the combination of polynite, bentonite, beidellite, canbyite, lithium soap soil or aforementioned substances.
7. modified stratified material as claimed in claim 1, wherein this layered inorganic material has the cationic exchange equivalent of about 50meq/100g to about 250meq/100g.
8. modified stratified material as claimed in claim 1, wherein the weight percent of this organic modifiers is that about 10 weight % are to about 20 weight %.
9. modified stratified material as claimed in claim 1, its interlayer spacing is greater than about 20 dusts.
10. unsaturated polyester nano composite material comprises:
Polymer matrix, it comprises unsaturated polyester resin; And
Modified stratified material as claimed in claim 1, wherein this modified stratified material is scattered in this polymer matrix and peels off at least in part.
11. unsaturated polyester nano composite material as claimed in claim 10, wherein the weight percent of this modified stratified material is that about 0.1 weight % is to about 7 weight %.
12. unsaturated polyester nano composite material as claimed in claim 10, wherein the weight percent of this modified stratified material is about 3 weight %.
13. unsaturated polyester nano composite material as claimed in claim 10, its volumetric shrinkage is littler by about 2% to about 11% than the polymer matrix that does not comprise this modified stratified material.
14. unsaturated polyester nano composite material as claimed in claim 10, its evenly heat release rate is than the little about 90kW/m of the polymer matrix that does not comprise this modified stratified material
2To about 410kW/m
2
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893260A (en) * | 2015-05-26 | 2015-09-09 | 苏州宏恒化工有限公司 | Preparation method of PET composite for packaging tape |
| CN106189371A (en) * | 2016-07-11 | 2016-12-07 | 滁州格锐矿业有限责任公司 | A kind of modified micaceous powder and preparation method thereof |
| CN109517354A (en) * | 2018-11-22 | 2019-03-26 | 安徽汇创新材料有限公司 | A kind of fire-retardant resistance to compression composite material and preparation method for glass toughening manure pit |
| CN113461966A (en) * | 2021-08-23 | 2021-10-01 | 濮阳市盛源能源科技股份有限公司 | Flame-retardant unsaturated polyester resin and preparation method thereof |
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2009
- 2009-06-18 CN CN2009101461875A patent/CN101928477A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893260A (en) * | 2015-05-26 | 2015-09-09 | 苏州宏恒化工有限公司 | Preparation method of PET composite for packaging tape |
| CN104893260B (en) * | 2015-05-26 | 2016-12-07 | 海门市彼维知识产权服务有限公司 | A kind of preparation method of the PET composite material for strap |
| CN106189371A (en) * | 2016-07-11 | 2016-12-07 | 滁州格锐矿业有限责任公司 | A kind of modified micaceous powder and preparation method thereof |
| CN109517354A (en) * | 2018-11-22 | 2019-03-26 | 安徽汇创新材料有限公司 | A kind of fire-retardant resistance to compression composite material and preparation method for glass toughening manure pit |
| CN113461966A (en) * | 2021-08-23 | 2021-10-01 | 濮阳市盛源能源科技股份有限公司 | Flame-retardant unsaturated polyester resin and preparation method thereof |
| CN113461966B (en) * | 2021-08-23 | 2022-07-26 | 濮阳市盛源能源科技股份有限公司 | Flame-retardant unsaturated polyester resin and preparation method thereof |
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Application publication date: 20101229 |