CN1300205C - One-step synthesis of bisphenol linear bakelite containing cyclanes - Google Patents
One-step synthesis of bisphenol linear bakelite containing cyclanes Download PDFInfo
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- CN1300205C CN1300205C CNB2005100153703A CN200510015370A CN1300205C CN 1300205 C CN1300205 C CN 1300205C CN B2005100153703 A CNB2005100153703 A CN B2005100153703A CN 200510015370 A CN200510015370 A CN 200510015370A CN 1300205 C CN1300205 C CN 1300205C
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- bisphenol
- cycloalkane
- bis
- methyl
- novolac resin
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Abstract
本发明公开了一种一步合成含环烷烃双酚线性酚醛树脂的方法。该方法制备过程包括：以多聚醛和含环烷烃双酚化合物为原料，投料比为2∶1～5∶1；再加入与含环烷烃双酚摩尔比为0.1∶1～0.4∶1的氢氧化钠催化剂，最后加入与含环烷烃双酚摩尔比为1∶12～1∶16的无水乙醇或无水甲醇作为溶剂。在搅拌下反应温度控制在70℃～80℃，反应1h～4h，生成含环烷烃双酚线性酚醛树脂化合物粗产品，再经水洗、过滤，直至水洗至中性，最终制得含环烷烃双酚类线性酚醛树脂。本发明的优点在于操作过程简便，制得的线性酚醛树脂分子量较大，凝聚力较大，在导电填料其中有较高的填充率，提高了其导电性能。The invention discloses a method for synthesizing cycloalkane-containing bisphenol novolac resin in one step. The preparation process of the method comprises: using polyaldehyde and cycloalkane-containing bisphenol compound as raw materials, the feeding ratio is 2:1-5:1; Sodium hydroxide catalyst, and finally adding anhydrous ethanol or anhydrous methanol with a molar ratio of 1:12 to 1:16 to bisphenol containing cycloalkane as a solvent. The reaction temperature is controlled at 70°C to 80°C under stirring, and the reaction is carried out for 1h to 4h to generate a crude product of cycloalkane-containing bisphenol novolac resin compound, which is then washed with water and filtered until it is washed to neutrality, and finally the naphthene-containing bisphenol is obtained. Phenolic novolac resins. The invention has the advantages of simple and convenient operation process, the obtained novolac resin has relatively large molecular weight and large cohesive force, has relatively high filling rate in the conductive filler, and improves its conductive performance.
Description
Technical field
The invention relates to the method that a kind of one-step synthesis contains bad alkane bisphenol linear resol, belong to the technology of preparing of bisphenol linear resol.
Background technology
The bisphenol A-type linear phenolic resin is the preferable resin systems of over-all properties such as a kind of thermotolerance, water tolerance, anti-ion transport, color and luster, applied range, can be used as solidifying agent, film-forming resin, in field produces as the topcoating of oil and water well sand-control resin precoated sand and as the matrix resin of conductive coating.At present, such linear phenolic resin is a raw material with straight chain aldehydes or ketones and bisphenol compound mainly, adopts two step method synthesis technique .JP63-30579 such as () meal Tian Yixi promptly to synthesize the hydroxymethyl phenol condenses earlier under base catalysis, and then reacts with sylvic acid.Because two-step synthesis technology relates to the pickling and the washing of phenolic condensation compound, the three wastes are many, and labour intensity is big.
Summary of the invention
The object of the present invention is to provide a kind of one-step synthesis to contain the method for naphthenic hydrocarbon bisphenol linear resol, this procedure is simple, and it is good to make the resol mechanical property, and light transmission is better, and stability increases substantially.
The present invention is realized that by following technical proposals a kind of one-step synthesis contains the method for naphthenic hydrocarbon bisphenol linear resol, and its feature comprises following process:
(1). with the monomer of Paraformaldehyde 96, Metaldehyde or metapropionaldehyde with contain the naphthenic hydrocarbon bis-phenol and added in 2: 1 in molar ratio～5: 1 and be equipped with in the reactor of whipping appts, adding with containing naphthenic hydrocarbon bis-phenol mol ratio again is 0.1: 1～0.4: 1 sodium hydroxide catalyst, and adding with containing naphthenic hydrocarbon bis-phenol mol ratio at last is that 1: 12～1: 16 dehydrated alcohol or anhydrous methanol are as solvent.Under agitation temperature of reaction is controlled at 70 ℃～80 ℃, and reaction 1h～4h obtains light yellow thick liquid.
(2). the light yellow thick liquid that step (1) is made filters, and filtrate is carried out underpressure distillation, removes dehydrated alcohol or anhydrous methanol in the filtrate, and the little yellow transparent dope of gained is thick product.Through washing, be washed to neutrality again, filter, finally make and contain naphthenic hydrocarbon bisphenol linear resol.
The above-mentioned naphthenic hydrocarbon bis-phenol that contains is 1,1-two (3 methyl-4-hydroxy phenyl) hexanaphthene, 1,1-two (4-hydroxy phenyl) pentamethylene, 1,1-two (3-methyl-4-hydroxy phenyl) pentamethylene, 1,1-two (3,5-dimethyl-4-hydroxy phenyl) suberane or 1,1-two (2-methyl-4-hydroxy phenyl)-3-methylcyclohexane.
The present invention has the easy characteristics of operating process, and prepared product is applied in the conductive coating, and is bigger with its molecular weight, the filling ratio that cohesive force is bigger and higher, thus improved conductivity, mechanical property and the light transmission of conductive coating.
Embodiment
Example 1
1,1-two (4-hydroxy phenyl) hexanaphthene linear phenolic resin synthetic:
In being housed, the 500mL four-hole bottle of reflux condensing tube, thermometer and agitator adds 26.8g (0.1mol) 1,1-two (4-hydroxy phenyl) hexanaphthene, 12g (0.4mol) Paraformaldehyde 96 (pressing formaldehyde conversion molar weight), 80mL dehydrated alcohol.Temperature of reaction is controlled at 75 ℃～80 ℃, reaction 4h, and whole process stirs with 200r/min～400r/min.With the light yellow solid material underpressure distillation (vacuum tightness is 0.09MPa) that makes, the little yellow transparent solid of gained is thick product.Repeatedly wash, filter with distilled water,, finally make 1 until being washed to neutrality, 1-two (4-hydroxy phenyl) hexanaphthene linear phenolic resin 33.25g, yield is 85.7%.Recording viscosity in 50% ethanolic soln is 980mPaS, and molecular weight is 2400.
Example 2
1,1-two (3-methyl-4-hydroxy phenyl) hexanaphthene linear phenolic resin synthetic:
In being housed, the 500mL four-hole bottle of reflux condensing tube, thermometer and agitator adds 29.6g (0.1mol) 1,1-two (3-methyl-4-hydroxy phenyl) hexanaphthene, 12g (0.4mol) Paraformaldehyde 96 (pressing formaldehyde conversion molar weight), 80mL dehydrated alcohol.Temperature of reaction is controlled at 75 ℃～80 ℃, reaction 4h, and whole process stirs with 200r/min～400r/min.With the light yellow solid material underpressure distillation (vacuum tightness is 0.09MPa) that makes, the little yellow transparent solid of gained is thick product.Repeatedly wash, filter with distilled water,, finally make 1 until being washed to neutrality, 1-two (3-methyl-4-hydroxy phenyl) hexanaphthene linear phenolic resin 35.9g, yield is 86.3%.Recording viscosity in 50% ethanolic soln is 1400mPaS, and molecular weight is 4100.
Example 3
1,1-two (4-hydroxy phenyl) pentamethylene linear phenolic resin synthetic:
In being housed, the 500mL four-hole bottle of reflux condensing tube, thermometer and agitator adds 25.6g (0.1mol) 1,1-two (4-hydroxy phenyl) pentamethylene, 12g (0.4mol) Paraformaldehyde 96 (pressing formaldehyde conversion molar weight), 80mL dehydrated alcohol.Temperature of reaction is controlled at 70 ℃～75 ℃, reaction 4h, and whole process stirs with 200r/min～400r/min.With the light yellow solid material underpressure distillation (vacuum tightness is 0.09MPa) that makes, the little yellow transparent solid of gained is thick product.Repeatedly wash, filter with distilled water,, finally make 1 until being washed to neutrality, 1-two (4-hydroxy phenyl) pentamethylene linear phenolic resin 31.7g, yield is 84.3%.Recording viscosity in 50% ethanolic soln is 860mPaS, and molecular weight is 1800.
Example 4
1,1-two (3-methyl-4-hydroxy phenyl) pentamethylene linear phenolic resin synthetic:
In being housed, the 500mL four-hole bottle of reflux condensing tube, thermometer and agitator adds 28.2g (0.1mol) 1,1-two (3-methyl-4-hydroxy phenyl) pentamethylene, 12g (0.4mol) Paraformaldehyde 96 (pressing formaldehyde conversion molar weight), 80mL dehydrated alcohol.Temperature of reaction is controlled at 75 ℃～80 ℃, reaction 4h, and whole process stirs with 200r/min～400r/min.With the light yellow solid material underpressure distillation (vacuum tightness is 0.09MPa) that makes, the little yellow transparent solid of gained is thick product.Repeatedly wash, filter with distilled water,, finally make 1 until being washed to neutrality, 1-two (3-methyl-4-hydroxy phenyl) pentamethylene linear phenolic resin 34.2g, yield is 85.1%.Recording viscosity in 50% ethanolic soln is 1050mPaS, and molecular weight is 2700.
Example 5
1,1-two (3,5-dimethyl-4-hydroxy phenyl) suberane linear phenolic resin synthetic:
In being housed, the 500mL four-hole bottle of reflux condensing tube, thermometer and agitator adds 33.8g (0.1mol) 1,1-two (3,5-dimethyl-4-hydroxy phenyl) suberane, 12g (0.4mol) Paraformaldehyde 96 (pressing formaldehyde conversion molar weight), 80mL dehydrated alcohol.Temperature of reaction is controlled at 75 ℃～80 ℃, reaction 4h, and whole process stirs with 200r/min～400r/min.With the light yellow solid material underpressure distillation (vacuum tightness is 0.09MPa) that makes, the little yellow transparent solid of gained is thick product.With distilled water repeatedly wash, filter, drying, until being washed to neutrality, finally make 1,1-two (3,5-dimethyl-4-hydroxy phenyl) suberane linear phenolic resin 38.5g, yield is 84.1%.Recording viscosity in 50% ethanolic soln is 1700mPaS, and molecular weight is 6700.
Example 6
1,1-two (2-methyl-4-hydroxy phenyl)-3-methylcyclohexane linear phenolic resin synthetic:
In being housed, the 500mL four-hole bottle of reflux condensing tube, thermometer and agitator adds 31.0g (0.1mol) 1,1-two (2-methyl-4-hydroxy phenyl)-3-methylcyclohexane, 12g (0.4mol) Paraformaldehyde 96 (pressing formaldehyde conversion molar weight), 80mL dehydrated alcohol.Temperature of reaction is controlled at 75 ℃～80 ℃, reaction 4h, and whole process stirs with 200r/min～400r/min.With the light yellow solid material underpressure distillation (vacuum tightness is 0.09MPa) that makes, the little yellow transparent solid of gained is thick product.With distilled water repeatedly wash, filter, drying, until being washed to neutrality, finally make 1,1-two (2-methyl-4-hydroxy phenyl)-3-methylcyclohexane linear phenolic resin 35.6g, yield is 82.8%.Recording viscosity in 50% ethanolic soln is 1450mPaS, and molecular weight is 4600.
Example 7
With 1.5g SnO
2-Sb
2O
3Composite conductive powder, 5ml dehydrated alcohol, 0.1g tetrabutyl titanate, granulated glass sphere 15g put into 2h (300r/min) ball mill, ball milling 30min.Contain naphthenic hydrocarbon bis-phenol resol, ball milling 90min to what wherein add 5ml dehydrated alcohol and 3.5g by what example 2 made again.Gained liquid is coated with in surface of aluminum plate, 150 ℃ of oven dry 30min.Body resistivity is between 10
8～10
9Ω cm.
Example 8:
With 4g SnO
2-Sb
2O
3Composite conductive powder, 5ml dehydrated alcohol, 0.1g tetrabutyl titanate, granulated glass sphere 15g put into 2h (300r/min) ball mill, ball milling 30min.Contain naphthenic hydrocarbon bis-phenol resol, ball milling 90min to what wherein add 5ml dehydrated alcohol and 3.5g by what example 4 made again.Gained liquid is coated with in surface of aluminum plate, 150 ℃ of oven dry 30min.Body resistivity≤10
3Ω cm.
Example 9:
With 1.5g SnO
2-Sb
2O
3Composite conductive powder, 5ml dehydrated alcohol, 0.1g tetrabutyl titanate, granulated glass sphere 15g put into 2h (300r/min) ball mill, ball milling 30min.Contain naphthenic hydrocarbon bis-phenol resol, ball milling 90min to wherein adding 5ml dehydrated alcohol and 3.0g by what example 6 made again.Gained liquid is coated with in surface of aluminum plate, 150 ℃ of oven dry 30min.Zhi Bei conductive coating has good flowability and solvent resistance with this understanding.Body resistivity is 8.2 * 10
8Ω cm, thickness 12 μ m satisfy processing requirement (body resistivity≤10
9Ω cm, thickness 5～50 μ m).
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100153703A CN1300205C (en) | 2005-10-13 | 2005-10-13 | One-step synthesis of bisphenol linear bakelite containing cyclanes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100153703A CN1300205C (en) | 2005-10-13 | 2005-10-13 | One-step synthesis of bisphenol linear bakelite containing cyclanes |
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| Publication Number | Publication Date |
|---|---|
| CN1746202A CN1746202A (en) | 2006-03-15 |
| CN1300205C true CN1300205C (en) | 2007-02-14 |
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| CNB2005100153703A Expired - Fee Related CN1300205C (en) | 2005-10-13 | 2005-10-13 | One-step synthesis of bisphenol linear bakelite containing cyclanes |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330579A (en) * | 1986-07-25 | 1988-02-09 | Toyo Ink Mfg Co Ltd | Printing ink resin |
| CN1183421A (en) * | 1995-10-30 | 1998-06-03 | 群荣化学工业株式会社 | Novolac resin and method for producing the same |
| CN1639217A (en) * | 2001-11-16 | 2005-07-13 | 旭有机材工业株式会社 | Phenolic novolaks and process for production thereof |
| CN1646628A (en) * | 2002-04-11 | 2005-07-27 | Az电子材料日本株式会社 | Novolac resin mixture and photosensitive composition containing it |
-
2005
- 2005-10-13 CN CNB2005100153703A patent/CN1300205C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330579A (en) * | 1986-07-25 | 1988-02-09 | Toyo Ink Mfg Co Ltd | Printing ink resin |
| CN1183421A (en) * | 1995-10-30 | 1998-06-03 | 群荣化学工业株式会社 | Novolac resin and method for producing the same |
| CN1639217A (en) * | 2001-11-16 | 2005-07-13 | 旭有机材工业株式会社 | Phenolic novolaks and process for production thereof |
| CN1646628A (en) * | 2002-04-11 | 2005-07-27 | Az电子材料日本株式会社 | Novolac resin mixture and photosensitive composition containing it |
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| Publication number | Publication date |
|---|---|
| CN1746202A (en) | 2006-03-15 |
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Kingboard (Fogang) Laminate Plate Co., Ltd. Assignor: Tianjin University Contract record no.: 2010440000469 Denomination of invention: One-step synthesis of bisphenol linear bakelite containing cyclanes Granted publication date: 20070214 License type: Exclusive License Open date: 20060315 Record date: 20100505 |
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| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Kingboard (Fogang) Laminate Plate Co., Ltd. Assignor: Tianjin University Contract record no.: 2010440000469 Date of cancellation: 20120926 |
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