CN102167896A - Recessive evocating agent and a method for preparing the same and a kind of artificial stone - Google Patents
Recessive evocating agent and a method for preparing the same and a kind of artificial stone Download PDFInfo
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- CN102167896A CN102167896A CN 201010603363 CN201010603363A CN102167896A CN 102167896 A CN102167896 A CN 102167896A CN 201010603363 CN201010603363 CN 201010603363 CN 201010603363 A CN201010603363 A CN 201010603363A CN 102167896 A CN102167896 A CN 102167896A
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- initiator
- unsaturated polyester
- polyester resin
- evocating agent
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- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 title abstract 12
- 239000002969 artificial stone Substances 0.000 title abstract 2
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 50
- 239000003999 initiator Substances 0.000 claims description 92
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000499 gel Substances 0.000 claims description 19
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical group CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012615 aggregate Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 abstract description 12
- 230000008023 solidification Effects 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 29
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- 239000005995 Aluminium silicate Substances 0.000 description 12
- 235000012211 aluminium silicate Nutrition 0.000 description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 12
- 239000012496 blank sample Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a recessive evocating agent, Being composed of unsaturated polyester resin and evocating agent, Wherein the evocating agent is 5% to 19% of unsaturated polyester resin in weight, The present invention also discloses a method for preparing the recessive evocating agent and a kind of artificial stone comprising the recessive evocating agent. The invention provided recessive evocating agent uses unsaturated polyester resin as carriers of the evocating agent, Adding excessive evocating agent into the unsaturated polyester resin, Adding caking agent in proportion into the unsaturated polyester resin, When the unsaturated polyester resin being solid, Reaching the excitation temperature, The evocating agent will be released from the powder, The reaction will be continued, As thus, a purpose of prolonging solidification time can be achieved. At the same time of prolonging reaction time, Presence of the evocating agent in the stage of later solidification can also be ensured, The solidification degree and comprehensive performance can also be improved.
Description
Technical field
The present invention relates to the resin solidification technical field, especially used hiding type initiator and preparation method thereof in the resin solidification; Also relate to the rostone that contains this hiding type initiator.
Background technology
The rostone product is compared with lithotome, has characteristics such as deal is light, the sheet material thickness is even, glossiness good, translucent effect is obvious, is widely used in various indoor and outdoor building decorations.Rostone is made waste material mainly by raw materials such as aggregate, binding agent (being generally unsaturated polyester resin), pigment through batching, compacting, curing process, and waste material obtains sheet material via sawing operation, polishing.Wherein, the state of cure of resin has very big influence to the quality of stone material.
Polymer Physics studies show that, after fixing, and after promptly temperature rose to second-order transition temperature during resin solidification, curing reaction was still being proceeded, and can improve degree of cure like this.Find that in the rubber of lower crosslink density cross-linking density is high more and there is report to show, it is many more to bear the molecular chain that meets, and intensity is also just high more, and the high elastic deformation amount is more little, and the deformation that influenced by extraneous factor is more little.Equally, high more its over-all properties of the degree of cure of resin is good more in the rostone.For actual production, the proper extension curing reaction time also helps improving production efficiency, as the resin and the aggregate that remain in the stirring tank have the enough time to clear up, and reduces labour intensity etc.For this reason, be necessary studying aspect prolongation set time and the raising degree of cure.
To prolonging the long period of experiments research of set time, determined initiator to be hidden to achieve the goal.And initiator is hiding, can be divided into chemical hiding with physics and hide, and chemistry hides and comprises that change methylethyl ketone peroxide active ingredient ratio, coordinative solvent cage cover or the like; Physics is hiding generally to be that initiator is hidden in the inertia porous material, and initiator is discharged from hole in the stage lentamente at after fixing, reaches the purpose that prolongs set time.What porous material commonly used adopted is kaolin, working method is as follows: add competent organic solvent in a certain amount of initiator it is fully dissolved, adding kaolin in mixed solution fully stirs, vacuumize under the normal temperature then, organic solvent is volatilized fully, and promptly mixture only contains kaolin and initiator.An initiator part is in the kaolin surface attachment, and another part then hides in kaolinic hole.
According to the method, generally obtain initiator content and be about 4.78% kaolin, this kaolin that has initiator is added in the resin, adjustment adds the amount of initiator and kaolin introducing initiator, make its total content identical with blank sample, according to actual production operating process pressing plate, guarantee that the pressing plate process condition is consistent then.Record the kaolinic sample of adding and compare with parallel blank sample, solidifying the time-delay rate is 293%, and intensity improving rate 5% illustrates that this method can satisfy requirement of experiment to a certain extent.
But the kaolin of hiding initiator mixes in the unsaturated polyester resin, carries out temperature and follows the tracks of solidification process, draws out the exothermic peak curve of thinking usefulness.Find near curve slope fast rise 50～60 ℃, illustrate that curing reaction is violent suddenly, thereby obtain conclusion, hiding initiator begins to discharge from hole at this moment, and the firm gelling temp of resin this moment begins to rise but does not reach maximum, be exposed to outer initiator and increase suddenly, make resin internal portion zone fast, unfavorable to solidifying.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, propose a kind of raising initiator release temperature, prolong the hiding type initiator of resin solidification time.
In order to realize the foregoing invention purpose, the invention provides following technical scheme: a kind of hiding type initiator, constitute by unsaturated polyester resin and initiator, wherein the weight of initiator is 5%～19% of unsaturated polyester resin weight.
Preferably, the weight of described initiator is 10%～19% of unsaturated polyester resin weight.
Preferably, described initiator is a methylethyl ketone peroxide.
Compared with prior art, the present invention utilizes the carrier of unsaturated polyester resin as initiator, in unsaturated polyester resin, add excessive initiator, to be unsaturated polyester resin consume when curing reaction takes place a certain amount of initiator (in the production actual amount of initiator be generally resin 1%), the amount of initiator that the present invention added is much larger than this consumption; Therefore initiator can not participated in reaction fully, have in the product after remaining initiator is fixed on curing reaction, and these initiators can only exist in two ways: a kind ofly activate into free radical but be not consumed in addition in curing reaction, another kind is not participate in reaction fully to keep not changing.
The hiding type initiator cured block that the present invention obtains is worn into powder, add in proportion in the unsaturated polyester resin as binding agent, the amount of adding can guarantee that wherein amount of initiator enough keeps reaction to carry out fully.Add an amount of promotor simultaneously, when unsaturated polyester resin solidified, when reaching excitation temperature, initiator discharged from powder, and reaction is proceeded, and so just reached the purpose that prolongs set time.When prolonging the reaction times, also having guaranteed has initiator to exist in the after fixing stage, improves the over-all properties of degree of cure and product.
The present invention also provides the preparation method of hiding type initiator, comprises following process: add initiator and promotor in unsaturated polyester resin, stirring and evenly mixing forms at 12 ℃～15 ℃ gels; The weight of described adding initiator is 6%～20% of unsaturated polyester resin weight; The weight of described adding promotor is 0.02%～0.1% of unsaturated polyester resin weight.
Preferably, the rotating speed of described stirring is 110 commentaries on classics/min.
The present invention also provides the rostone that adopts above-mentioned hiding type initiator, comprise by aggregate, binding agent and pigment and making, it is characterized in that: this rostone also comprises the hiding type initiator that is made of unsaturated polyester resin and initiator, and wherein initiator is 5%～19% of a unsaturated polyester resin weight; The consumption of described hiding type initiator is counted 1% of binding agent by initiator.
Preferably, described binding agent is a unsaturated polyester resin.
The hiding type initiator of the present invention compares with the hiding type initiator that utilizes kaolin as carrier, and it has following advantage:
1, the initiator release temperature is higher.According to the resin solidification exothermic peak curve of drawing as can be known, powder discharges the initiator temperature and is about 110 ℃, 50～60 ℃ have been improved than kaolinic, promptly just discharge to the hiding initiator of certain phase at the unsaturated polyester resin curing reaction, guarantee to still have initiator to participate in reaction in the after fixing stage, prolong set time, improve degree of cure;
2, operation is simple.Kaolin will vacuumize as the production method operation more complicated of the hiding type initiator of carrier, and this operation is had relatively high expectations relatively and large-scale production realizes not too easily; And the making method of the hiding type initiator of the present invention is relatively just simple a lot, only need can obtain in the following curing of low temperature (12 ℃～15 ℃) in advance, adopt under this low temperature and to solidify, guarantee that unsaturated polyester resin can not emit big calorimetric and decompose rotten because of the too violent short period of time of reaction;
3, pollution-free, nothing adds cost.Because will handle acetone soln in the production method of kaolin as the hiding type initiator of carrier as solvent, might pollute and endanger, perhaps needing to increase treatment facility increases cost, and there is not such problem in the present invention in making.
Embodiment
Describe the present invention below in conjunction with specific embodiment, the description of this part only is exemplary and explanatory, should any restriction not arranged to protection scope of the present invention.
Embodiment 1
At first, take by weighing 100g and produce used unsaturated polyester resin, the promotor cobalt naphthenate that adds these unsaturated polyester resin 0.5 ‰ mass percents, change 20% the initiator methylethyl ketone peroxide that adds this unsaturated polyester resin weight after stirring again with electric mixer with per minute 110, stir with the same rotating speed of electric mixer.After stopping to stir recombined sample is cast in 55mm * 55mm * 15mm mould, place 15 ℃ to treat its gel, about 50min takes out behind the gel, (sample has slight cracking until the hardening slaking in the room temperature placement, do not have burned phenomenon), promptly make the latent initiator sample that size is about 55mm * 55mm * 15mm.
Then, break sample into pieces ball milling to required several 350 orders of aggregate level order, promptly obtain the hiding amount of initiator and be about 18% resin-oatmeal sample, the sealing stored for future use.(calculate by theoretical, unreacted initiator residual content should be 19% of unsaturated polyester resin weight, but all can give birth to heat in the sample bruting process, can cause a part of initiator activity forfeiture.)
At last, take by weighing the 100g unsaturated polyester resin, adding resin quality mark is 1 ‰ promotor, and electric mixer changes stirring 3min with per minute 110, add the above-mentioned prepared powder sample of 5.56g then, stirring is placed on the gel solidification time of detecting under 70 ℃ of constant temperature.This resin compound solidifies and prolongs effect such as following table 1, wherein adds the 1g initiator by the 100g unsaturated polyester resin, and blank sample is to add initiator; Currently available products is that kaolin is the hiding type initiator of carrier, down together.
The time-delay rate of three kinds of resin compound solidifying products of table 1 and degree of cure are relatively
| Resin g | Sample g | Initiator | Promotor | Gel time | The time-delay rate | Degree of cure | |
| Blank sample | ?100 | 0 | 1g | 0.1g | 45min | 0 | 88.95％ |
| Currently available products | ?100 | 20.9 | 0g | 0.1g | 132min | 193％ | 90.23％ |
| Embodiment 1 | ?100 | 5.56 | 0g | 0.1g | 135min | 200％ | 90.68％ |
Embodiment 2
This embodiment technology is identical with embodiment 1, but needs the unsaturated polyester resin consumption among the embodiment 1 is adjusted into 200g, and promotor cobalt naphthenate mass percent is adjusted into 1 ‰, and initiator methylethyl ketone peroxide mass percent is adjusted into 10%.By being cast in after embodiment 1 mixing and stirring in 55mm * 55mm * 30mm mould, place 12 ℃ to treat its gel, about 50min takes out behind the gel, (sample has slight cracking until the hardening slaking in the room temperature placement, do not have burned phenomenon), promptly make the latent initiator sample that size is about 55mm * 55mm * 30mm.
Then, break sample into pieces ball milling to required several 400 orders of aggregate level order, promptly obtain the hiding amount of initiator and be about 8% resin-oatmeal sample, the sealing stored for future use.
At last, take by weighing the 100g unsaturated polyester resin, adding resin quality mark is 1 ‰ promotor, electric mixer changes stirring 3min with per minute 110, add the above-mentioned prepared powder sample of 12.5g then, stir to be placed on and detect gel time under 70 ℃ of constant temperature, take out behind the gel 3h, survey degree of cure.This resin compound state of cure improves effect such as following table 2.
The time-delay rate of three kinds of resin compound solidifying products of table 2 and degree of cure are relatively
| Resin g | Sample g | Initiator | Promotor | Gel time | The time-delay rate | Degree of cure | |
| Blank sample | ?100 | 0 | 1g | 0.1g | 44min | 0 | 89.07％ |
| Currently available products | ?100 | 20.9 | 0 | 0.1g | 132min | 200％ | 90.23％ |
| Embodiment 2 | ?100 | 12.5 | 0 | 0.1g | 170min | 286％ | 91.21％ |
Embodiment 3
At first, take by weighing 50g and produce used unsaturated polyester resin, the promotor cobalt naphthenate that adds these unsaturated polyester resin 0.8 ‰ mass percents, change the initiator methylethyl ketone peroxide that adds this unsaturated polyester resin 12% mass percent after stirring again with electric mixer with per minute 110, stir with the same rotating speed of electric mixer.After stopping to stir recombined sample is cast in 55mm * 55mm * 15mm mould, place 13 ℃ to treat its gel, about 50min takes out behind the gel, (sample has slight cracking until the hardening slaking in the room temperature placement, do not have burned phenomenon), promptly make the latent initiator sample that size is about 55mm * 55mm * 15mm.
Then, break sample into pieces ball milling to required several 320 orders of aggregate level order, promptly obtain the hiding amount of initiator and be about 10% resin-oatmeal sample, the sealing stored for future use.
At last, take by weighing the 100g unsaturated polyester resin, adding resin quality mark is 1 ‰ promotor, and electric mixer changes stirring 3min with per minute 110, add the above-mentioned prepared powder sample of 10g then, stirring is placed on the gel solidification time of detecting under 70 ℃ of constant temperature.This resin compound solidifies and prolongs effect such as following table 3.
The time-delay rate of three kinds of products of table 3 and degree of cure are relatively
| Resin g | Sample g | Initiator | Promotor | Gel time | The time-delay rate | Degree of cure | |
| Blank sample | ?100 | 0 | 1g | 1‰ | 45min | 0 | 88.95％ |
| Currently available products | ?100 | 20.9 | 0g | 1‰ | 132min | 193％ | 90.23％ |
| Embodiment 3 | ?100 | 10 | 0g | 1‰ | 150min | 233％ | 91.28％ |
Embodiment 4
At first, take by weighing 150g and produce used unsaturated polyester resin, the promotor cobalt naphthenate that adds these unsaturated polyester resin 0.7 ‰ mass percents, change the initiator methylethyl ketone peroxide that adds this unsaturated polyester resin 7% mass percent after stirring again with electric mixer with per minute 110, stir with the same rotating speed of electric mixer.After stopping to stir recombined sample is cast in 55mm * 55mm * 15mm mould, place 13 ℃ to treat its gel, about 50min takes out behind the gel, (sample has slight cracking until the hardening slaking in the room temperature placement, do not have burned phenomenon), promptly make the latent initiator sample that size is about 55mm * 55mm * 15mm.
Then, break sample into pieces ball milling to required several 340 orders of aggregate level order, promptly obtain the hiding amount of initiator and be about 5% resin-oatmeal sample, the sealing stored for future use.
At last, take by weighing the 100g unsaturated polyester resin, adding resin quality mark is 1 ‰ promotor, and electric mixer changes stirring 3min with per minute 110, add the above-mentioned prepared powder sample of 10g then, stirring is placed on the gel solidification time of detecting under 70 ℃ of constant temperature.This resin compound solidifies and prolongs effect such as following table 4.
The time-delay rate of three kinds of products of table 4 and degree of cure are relatively
| Resin g | Sample g | Initiator | Promotor | Gel time | The time-delay rate | Degree of cure | |
| Blank sample | ?100 | 0 | 1g | 1‰ | 45min | 0 | 88.95％ |
| Currently available products | ?100 | 20.9 | 0g | 1‰ | 132min | 293％ | 90.23％ |
| Embodiment 4 | ?100 | 5 | 0g | 1‰ | 148min | 329％ | 91.06％ |
The test example
The type initiator is hidden in embodiment 1 to embodiment 4 prepared containing, the process for preparing rostone according to routine, with aggregate, unsaturated polyester resin, pigment and promotor, make waste material through batching, compacting, curing process, waste material obtains artificial slabstone via polishing, sawing operation.
Detect the intensity of three prepared rostones of embodiment, see the following form 4;
The folding strength of table 4 rostone
| Folding strength | Intensity improving rate | |
| Blank sample | 35.45Mpa | - |
| Currently available products | 37.22MPa | 5％ |
| Embodiment 1 | 39.35MPa | 11％ |
| Embodiment 2 | 38.25MPa | 8％ |
| Embodiment 3 | 39.0MPa | 10％ |
| Embodiment 4 | 39.21MPa | 11％ |
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a hiding type initiator is made of unsaturated polyester resin and initiator, and wherein the weight of initiator is 5%～19% of unsaturated polyester resin weight.
2. hiding type initiator as claimed in claim 1 is characterized in that: the weight of described initiator is 10%～19% of unsaturated polyester resin weight.
3. hiding type initiator as claimed in claim 1 or 2 is characterized in that: described initiator is a methylethyl ketone peroxide.
4. the preparation method of a hiding type initiator comprises following process: add initiator and promotor in unsaturated polyester resin, stirring and evenly mixing forms at 12 ℃～15 ℃ gels; The weight of described adding initiator is 6%～20% of unsaturated polyester resin weight; The weight of described adding promotor is 0.02%～0.1% of unsaturated polyester resin weight.
5. preparation method as claimed in claim 4 is characterized in that: described initiator is a methylethyl ketone peroxide.
6. preparation method as claimed in claim 4 is characterized in that: described promotor is cobalt naphthenate.
7. preparation method as claimed in claim 4 is characterized in that: the rotating speed of described stirring is 110 commentaries on classics/min.
8. a rostone comprises by aggregate, binding agent and pigment and making, and it is characterized in that: this rostone also comprises the hiding type initiator that is made of unsaturated polyester resin and initiator, and wherein initiator is 5%～19% of a unsaturated polyester resin weight; The consumption of described hiding type initiator is counted 1% of binding agent by initiator.
9. rostone as claimed in claim 8 is characterized in that: described binding agent is a unsaturated polyester resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010603363 CN102167896B (en) | 2010-12-23 | 2010-12-23 | Recessive initiator and a method for preparing the same and a kind of artificial stone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010603363 CN102167896B (en) | 2010-12-23 | 2010-12-23 | Recessive initiator and a method for preparing the same and a kind of artificial stone |
Publications (2)
| Publication Number | Publication Date |
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| CN102167896A true CN102167896A (en) | 2011-08-31 |
| CN102167896B CN102167896B (en) | 2013-03-13 |
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| CN 201010603363 Expired - Fee Related CN102167896B (en) | 2010-12-23 | 2010-12-23 | Recessive initiator and a method for preparing the same and a kind of artificial stone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117487180A (en) * | 2023-11-07 | 2024-02-02 | 苏州优矿塑新材料股份有限公司 | Kaolin intercalation composite material based on in-situ grafting reaction and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166230A (en) * | 1991-09-16 | 1992-11-24 | Stecker William M | Method for producing a synthetic shaped article simulating marble, granite or the like |
| CN101245192A (en) * | 2007-02-15 | 2008-08-20 | 中国船舶重工集团公司第七二五研究所 | A method of manufacturing basalt fiber reinforced composite material and its application in manufacturing ship hulls |
| CN101289572A (en) * | 2008-06-16 | 2008-10-22 | 山东大学 | Unsaturated resin brittle material convenient for pre-setting built-in cracks and method for preparing test piece |
| CN101605847A (en) * | 2006-12-29 | 2009-12-16 | 库克复合材料和聚合物公司 | Organic powder fillers that can be used instead of mineral fillers in composite materials |
-
2010
- 2010-12-23 CN CN 201010603363 patent/CN102167896B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166230A (en) * | 1991-09-16 | 1992-11-24 | Stecker William M | Method for producing a synthetic shaped article simulating marble, granite or the like |
| CN101605847A (en) * | 2006-12-29 | 2009-12-16 | 库克复合材料和聚合物公司 | Organic powder fillers that can be used instead of mineral fillers in composite materials |
| CN101245192A (en) * | 2007-02-15 | 2008-08-20 | 中国船舶重工集团公司第七二五研究所 | A method of manufacturing basalt fiber reinforced composite material and its application in manufacturing ship hulls |
| CN101289572A (en) * | 2008-06-16 | 2008-10-22 | 山东大学 | Unsaturated resin brittle material convenient for pre-setting built-in cracks and method for preparing test piece |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117487180A (en) * | 2023-11-07 | 2024-02-02 | 苏州优矿塑新材料股份有限公司 | Kaolin intercalation composite material based on in-situ grafting reaction and preparation method thereof |
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| C56 | Change in the name or address of the patentee |
Owner name: WANFENG COMPOUND STONE TECHNOLOGY CO., LTD. Free format text: FORMER NAME: WANFENG STONE MATERIAL SCIENCE AND TECHNOLOGY CO., LTD. |
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| CP01 | Change in the name or title of a patent holder |
Address after: 528308 Guangdong city of Foshan Province, Shunde District Lunjiao North Development Zone Three delta Longzhou Road No. four or five block Patentee after: WANFENG COMPOUND STONE TECHNOLOGY Co.,Ltd. Address before: 528308 Guangdong city of Foshan Province, Shunde District Lunjiao North Development Zone Three delta Longzhou Road No. four or five block Patentee before: Wanfeng Compound Stone Technology Co.,Ltd. |
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| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 517583 Guangdong Xian Heyuan Dongyuan Xian Tang Town Industrial Park (Guangdong high micro crystal technology Co., Ltd. factory building) Patentee after: WANFENG COMPOUND STONE TECHNOLOGY Co.,Ltd. Address before: 528308 block 3, four or five, Longzhou Road, Lun Jiao three Island Development Zone, Shunde District, Foshan, Guangdong Patentee before: WANFENG COMPOUND STONE TECHNOLOGY Co.,Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130313 |