CN102604040A - Method for preparing SiCNO foamed ceramics - Google Patents
Method for preparing SiCNO foamed ceramics Download PDFInfo
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- CN102604040A CN102604040A CN2012100743255A CN201210074325A CN102604040A CN 102604040 A CN102604040 A CN 102604040A CN 2012100743255 A CN2012100743255 A CN 2012100743255A CN 201210074325 A CN201210074325 A CN 201210074325A CN 102604040 A CN102604040 A CN 102604040A
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Abstract
The invention discloses a method for preparing SiCNO foamed ceramics and relates to a method for preparing the foamed ceramics. The invention aims to solve the problems of low strength and weak wear resistance of the existing silicon-containing polyurethane material. The method for preparing the foamed ceramics, which is disclosed by the invention, comprises the following steps of: 1, weighing a SiCNO precursor, diphenylmethane diisocyanate (MDI), polyether polyol and a foaming agent, mixing the SiCNO precursor and the MDI, uniformly stirring, adding the polyether polyol and the foaming agent and freely foaming to obtain foams; and 2, placing the foams into a crucible, transferring the crucible into a tube furnace, heating the tube furnace to 900 to 1,200 DEG C at the speed of 1 to 200 DEG C.h<-1> in the argon atmosphere and cooling to the room temperature to obtain the SiCNO foamed ceramics. The SiCNO foamed ceramics prepared by the method disclosed by the invention has low elasticity, the strength of the SiCNO foamed ceramics is improved so that the wear resistance of the SiCNO foamed ceramics is strengthened. The SiCNO foamed ceramics prepared by the method disclosed by the invention is used for the medical field.
Description
Technical field
The present invention relates to the preparation method of foamed ceramics.
Background technology
In medical field; People obtain siliceous polyurethane material through organosilyl grafting, modified method; Utilize organosilyl hydrophobic, anticoagulant property and high ventilation effect, be prepared as tissue and organs such as artificial skin, blood vessel, bladder, heart valve.But the content of silicon is lower in the existing siliceous polyurethane material, intensity is lower and limited its application.
Summary of the invention
The present invention will solve the existing siliceous problem that polyurethane material intensity is low, wear resistance is more weak, and a kind of preparation method of SiCNO foamed ceramics is provided.
The preparation method of SiCNO foamed ceramics of the present invention carries out according to the following steps:
One, be (0.5～1) in mass ratio: (1～3): (2～6): the ratio of (0.1～6) takes by weighing SiCNO precursor, diphenylmethanediisocyanate, polyether glycol and whipping agent; Earlier the SiCNO precursor is mixed with diphenylmethanediisocyanate; Add polyether glycol and whipping agent after stirring, obtain foams behind the free foaming;
Two, the foams that step 1 obtained place in the crucible and are transferred to tube furnace, under argon gas atmosphere, with 1～200 ℃ of h
-1Speed is heated to 900～1200 ℃, is cooled to room temperature then, obtains the SiCNO foamed ceramics.
The used SiCNO precursor of the present invention is to be prepared from the method in the Chinese patent 200910308985.3; Compare with traditional polysilazane; The isocyanate functional group of synthetic SiCNO precursor of the present invention has high chemically reactive, can react with multiple functional groups such as alcohol, hydroxyl, carboxylic acid, amino, borines.In the polyurethane industrial, people utilize polyol ethers and binary isocyanate reaction, prepare all kinds of shape foam materials.Utilize above-mentioned characteristic; Liquid phase SiCNO precursor siloxanes isocyanic ester is cooperated with polyether glycol, diphenylmethanediisocyanate (MDI) by a certain percentage; Under the effect of whipping agent, prepare the new shape polyurethane foam pottery that contains the double elements isocyanate functional group.
The invention has the beneficial effects as follows: the relative content of silicon is far above present applied siliceous polyurethane material in the SiCNO foamed ceramics of the present invention's preparation, and therefore, elasticity is low, intensity increases and wear resistance is strengthened.Simultaneously, its inner hole distributes big or small uneven, and this makes the SiCNO foamed ceramics become a kind of potential osseous tissue renovating material, and big hole is that the growth of osseous tissue provides good space.Through the process of foaming, can some medicines, phosphatic rock etc. be repaired useful inanimate matter material homodisperse to bone and are closed in the foam framework.
The prepared SiCNO foamed ceramics of the present invention is with a wide range of applications in medical field.
Description of drawings
Fig. 1 is the photo of the foams of embodiment one step 1 gained; Fig. 2 is the photo of the SiCNO foamed ceramics of embodiment one gained; Fig. 3 is the photo of the SiCNO foamed ceramics of embodiment two gained.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of this embodiment SiCNO foamed ceramics carries out according to the following steps:
One, be (0.5～1) in mass ratio: (1～3): (2～6): the ratio of (0.1～6) takes by weighing SiCNO precursor, diphenylmethanediisocyanate, polyether glycol and whipping agent; Earlier the SiCNO precursor is mixed with diphenylmethanediisocyanate; Add polyether glycol and whipping agent after stirring, obtain foams behind the free foaming;
Two, the foams that step 1 obtained place in the crucible and are transferred to tube furnace, under argon gas atmosphere, with 1～200 ℃ of h
-1Speed is heated to 900～1200 ℃, is cooled to room temperature then, obtains the SiCNO foamed ceramics.
The diphenylmethanediisocyanate of this embodiment (MDI), polyether glycol and whipping agent are the commercially available prod; The SiCNO precursor is to be prepared from the method in the Chinese patent 200910308985.3.
The relative content of silicon is far above present applied siliceous polyurethane material in the SiCNO foamed ceramics of this embodiment preparation, and therefore, elasticity is low, intensity increases and wear resistance is strengthened.Simultaneously, its inner hole distributes big or small uneven, and this makes the SiCNO foamed ceramics become a kind of potential osseous tissue renovating material, and big hole is that the growth of osseous tissue provides good space.Through the process of foaming, can some medicines, phosphatic rock etc. be repaired useful inanimate matter material homodisperse to bone and are closed in the foam framework.
The prepared SiCNO foamed ceramics of this embodiment is with a wide range of applications in medical field; This method also provides a kind of new method for the preparation of multiple foamed ceramicses such as New Si C, SiOC, SiBCN, SiBON, SiBN and BN, promptly gets final product through carrying out pyrolysis after using these ceramic liquid phase precursor and polyethers and corresponding isocyanate mixing.
Embodiment two: what this embodiment and embodiment one were different is: the preparation method of SiCNO precursor carries out according to the following steps:
One, takes by weighing 20～30 parts nitrogenous source, 90～110 parts solvent and 12～18 parts silicon source according to ratio of weight and number; Two, the solvent that nitrogenous source that step 1 is taken by weighing and step 1 take by weighing places reaction kettle; Behind the capping still reaction kettle is vacuumized; Charge into argon gas as shielding gas to reaction kettle again; In reaction kettle, add the silicon source then and react and obtain resultant, the temperature in the reaction kettle is 30～150 ℃, and the reaction times is 44～50h; Three, the resultant with step 2 carries out the vacuum filtration processing; The filtrating that then suction filtration is obtained changes in the vacuum rotation heating evaporation volumetric flask; Distill in the water-bath between 80～90 ℃ and handle 10～60min, stay the material in bottle to be the SiCNO precursor at last.
In this embodiment, said nitrogenous source is an ammonium carbamate; Said solvent is hexanaphthene, normal hexane, benzene, toluene, glycol dimethyl ether, diethylene glycol dimethyl ether or THF; Said silicon source is made up of a kind of in methyl ethylene dichlorosilane, vinyl dichlorosilane, vinyl trichloro silane, dimethyldichlorosilane(DMCS), dimethyl dichlorosilane (DMCS), METHYL TRICHLORO SILANE, the phenmethyl dichlorosilane or wherein several kinds.
The isocyanate functional group of this embodiment synthetic SiCNO precursor has high chemically reactive, can react with multiple functional groups such as alcohol, hydroxyl, carboxylic acid, amino, borines.
Embodiment three: what this embodiment was different with embodiment one or two is: be (0.6～0.8) in mass ratio in the step 1: (1.5～2.5): (3～5): the ratio of (1～4) takes by weighing SiCNO precursor, diphenylmethanediisocyanate, polyether glycol and whipping agent.Other is identical with embodiment one or two.
Embodiment four: what this embodiment was different with one of embodiment one to three is: polyether glycol described in the step 1 is that molecular weight is 400～4000 polyoxypropyleneglycol, polytetrahydrofuran diol, THF-propylene oxide copolymerization glycol or TriMethylolPropane(TMP) polyethers.Other is identical with one of embodiment one to three.
Embodiment five: what this embodiment was different with one of embodiment one to four is: whipping agent described in the step 1 is methylene dichloride, trichloromethane, normal hexane, Skellysolve A, sherwood oil, azo cpd, sulfonyl hydrazide or nitroso-group.Other is identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to five is: in the step 2 with 50～190 ℃ of h
-1Speed is heated to 1000～1100 ℃.Other is identical with one of embodiment one to five.
Adopt following examples to verify beneficial effect of the present invention:
Embodiment one:
The preparation method of present embodiment SiCNO foamed ceramics carries out according to the following steps:
One, be 1: 2: 4 in mass ratio: 2 ratio takes by weighing SiCNO precursor, MDI, polyethers BL-4110H and methylene dichloride whipping agent; Earlier the SiCNO precursor is mixed with MDI; Add polyethers BL-4110H and methylene dichloride whipping agent after stirring, obtain foams behind the free foaming;
Two, the foams that step 1 obtained place plumbago crucible and are transferred to tube furnace in argon atmospher, with 60 ℃ of h
-1Speed stop heating after being heated to 1100 ℃, cool to room temperature with the furnace, obtain the SiCNO foamed ceramics.
Polyethers BL-4110H in the present embodiment is available from Shenyang Jin Bilan chemical inc, and MDI is available from Shanghai Ba Fusi urethane ltd.
SiCNO precursor in the present embodiment is to be prepared from according to the method in the Chinese patent 200910308985.3, and its concrete steps are following: a, take by weighing 25 parts ammonium carbamate, 100 parts hexanaphthene and 16 parts methyl ethylene dichlorosilane according to ratio of weight and number; B, the hexanaphthene that takes by weighing among ammonium carbamate that takes by weighing among a and a is placed reaction kettle; Behind the capping still reaction kettle is vacuumized; Charge into argon gas as shielding gas to reaction kettle again; In reaction kettle, add the methyl ethylene dichlorosilane then and react and obtain resultant, the temperature in the reaction kettle is 50 ℃, and the reaction times is 48h; C, the resultant of step b is carried out vacuum filtration handle, the filtrating that then suction filtration is obtained changes in the vacuum rotation heating evaporation volumetric flask, distills in the water-bath between 85 ℃ and handles 40min, stays the material in bottle to be the SiCNO precursor at last.
Embodiment two:
The preparation method of present embodiment SiCNO foamed ceramics carries out according to the following steps:
One, be 1: 2: 4 in mass ratio: 2 ratio takes by weighing SiCNO precursor, MDI, polyethers BL-4110H and methylene dichloride whipping agent; Earlier the SiCNO precursor is mixed with MDI; Add polyethers BL-4110H and methylene dichloride whipping agent after stirring, obtain foams behind the free foaming;
Two, the foams that step 1 obtained place plumbago crucible and are transferred to tube furnace in argon atmospher, with 200 ℃ of h
-1Speed stop heating after being heated to 1100 ℃, cool to room temperature with the furnace, obtain the SiCNO foamed ceramics.
SiCNO precursor in the present embodiment is to be prepared from according to the method in the Chinese patent 200910308985.3, and its concrete steps are following: a, take by weighing 25 parts ammonium carbamate, 100 parts hexanaphthene and 16 parts methyl ethylene dichlorosilane according to ratio of weight and number; B, the hexanaphthene that takes by weighing among ammonium carbamate that takes by weighing among a and a is placed reaction kettle; Behind the capping still reaction kettle is vacuumized; Charge into argon gas as shielding gas to reaction kettle again; In reaction kettle, add the methyl ethylene dichlorosilane then and react and obtain resultant, the temperature in the reaction kettle is 50 ℃, and the reaction times is 48h; C, the resultant of step b is carried out vacuum filtration handle, the filtrating that then suction filtration is obtained changes in the vacuum rotation heating evaporation volumetric flask, distills in the water-bath between 85 ℃ and handles 40min, stays the material in bottle to be the SiCNO precursor at last.
Polyethers BL-4110H in the present embodiment is available from Shenyang Jin Bilan chemical inc, and MDI is available from Shanghai Ba Fusi urethane ltd.
Fig. 1 is the photo of the foams of embodiment one step 1 gained; Fig. 2 is the photo of the SiCNO foamed ceramics of embodiment one gained; Fig. 3 is the photo of the SiCNO foamed ceramics of embodiment two gained; To be two close foams of size carry out the contraction situation contrast after the pyrolysis with different temperature rise rates for Fig. 2 and Fig. 3.
Embodiment one adopts 60 ℃ of h
-1Temperature rise rate carry out gained SiCNO foamed ceramics after the pyrolysis density at 0.75 ± 0.10gcm
-3About, this foamed ceramics shows certain intensity.
At the pyrolysis temperature rise rate of cold zone reduction precursor, can significantly improve the pyrolysis crosslinking degree of precursor.If improve the pyrolysis temperature rise rate of foamed ceramics precursor at cold zone, then can improve its pyrolysis crosslinking degree, promote the contraction of foam precursor, and then reduce the porosity of foamed ceramics.
Embodiment two is with 200 ℃ of h
-1Be rapidly heated during the speed pyrolysis because the cold zone crosslinking degree descends, the shrinking percentage of foamed ceramics also declines to a great extent, density foam is at 0.15 ± 0.05gcm
-3About, horizontal and vertical dimensional contraction rate is all less than 20%.
The relative content of silicon is far above present applied siliceous polyurethane material in the SiCNO foamed ceramics of the present invention's preparation, and therefore, elasticity is low, intensity increases and wear resistance is strengthened.Simultaneously, its inner hole distributes big or small uneven, and this makes the SiCNO foamed ceramics become a kind of potential osseous tissue renovating material, and big hole is that the growth of osseous tissue provides good space.Through the process of foaming, can some medicines, phosphatic rock etc. be repaired useful inanimate matter material homodisperse to bone and are closed in the foam framework.
The prepared SiCNO foamed ceramics of the present invention is with a wide range of applications in medical field.
Claims (5)
1.SiCNO the preparation method of foamed ceramics is characterized in that the preparation method of SiCNO foamed ceramics carries out according to the following steps:
One, be (0.5～1) in mass ratio: (1～3): (2～6): the ratio of (0.1～6) takes by weighing SiCNO precursor, diphenylmethanediisocyanate, polyether glycol and whipping agent; Earlier the SiCNO precursor is mixed with diphenylmethanediisocyanate; Add polyether glycol and whipping agent after stirring, obtain foams behind the free foaming;
Two, the foams that step 1 obtained place in the crucible and are transferred to tube furnace, under argon gas atmosphere, with 1～200 ℃ of h
-1Speed is heated to 900～1200 ℃, is cooled to room temperature then, obtains the SiCNO foamed ceramics.
2. the preparation method of SiCNO foamed ceramics according to claim 1, it is characterized in that being (0.6～0.8) in mass ratio in the step 1: (1.5～2.5): (3～5): the ratio of (1～4) takes by weighing SiCNO precursor, diphenylmethanediisocyanate, polyether glycol and whipping agent.
3. the preparation method of SiCNO foamed ceramics according to claim 1 and 2 is characterized in that polyether glycol described in the step 1 is that molecular weight is 400～4000 polyoxypropyleneglycol, polytetrahydrofuran diol, THF-propylene oxide copolymerization glycol or TriMethylolPropane(TMP) polyethers.
4. the preparation method of SiCNO foamed ceramics according to claim 1 and 2 is characterized in that whipping agent described in the step 1 is methylene dichloride, trichloromethane, normal hexane, Skellysolve A, sherwood oil, azo cpd, sulfonyl hydrazide or nitroso-group.
5. the preparation method of SiCNO foamed ceramics according to claim 1 and 2 is characterized in that in the step 2 with 50～190 ℃ of h
-1Speed is heated to 1000～1100 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004048A (en) * | 2019-11-26 | 2020-04-14 | 国装新材料技术(江苏)有限公司 | SiC foamed ceramic, heat exchange tube based on SiC foamed ceramic and engine cooling protection device |
| CN111662541A (en) * | 2020-05-07 | 2020-09-15 | 北京宇航系统工程研究所 | Silicon-boron-nitrogen-alkane modified high-temperature-resistant polyurethane rubber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762989A (en) * | 2005-11-08 | 2006-04-26 | 浙江工业大学 | Semicarbazone synthesis method |
| CN101693618A (en) * | 2009-10-29 | 2010-04-14 | 哈尔滨工业大学 | SiCN(O)ceramic material and preparation method thereof |
| CN101700978A (en) * | 2009-11-11 | 2010-05-05 | 哈尔滨工业大学 | Method for preparing SiBCN(O) ceramic material |
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- 2012-03-20 CN CN2012100743255A patent/CN102604040A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762989A (en) * | 2005-11-08 | 2006-04-26 | 浙江工业大学 | Semicarbazone synthesis method |
| CN101693618A (en) * | 2009-10-29 | 2010-04-14 | 哈尔滨工业大学 | SiCN(O)ceramic material and preparation method thereof |
| CN101700978A (en) * | 2009-11-11 | 2010-05-05 | 哈尔滨工业大学 | Method for preparing SiBCN(O) ceramic material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004048A (en) * | 2019-11-26 | 2020-04-14 | 国装新材料技术(江苏)有限公司 | SiC foamed ceramic, heat exchange tube based on SiC foamed ceramic and engine cooling protection device |
| CN111662541A (en) * | 2020-05-07 | 2020-09-15 | 北京宇航系统工程研究所 | Silicon-boron-nitrogen-alkane modified high-temperature-resistant polyurethane rubber and preparation method thereof |
| CN111662541B (en) * | 2020-05-07 | 2022-05-24 | 北京宇航系统工程研究所 | Silicon-boron-nitrogen-alkane modified high-temperature-resistant polyurethane rubber and preparation method thereof |
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Application publication date: 20120725 |