CN101768326A - Preparation method of modified phenolic resin and application thereof - Google Patents
Preparation method of modified phenolic resin and application thereof Download PDFInfo
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- CN101768326A CN101768326A CN201010022837A CN201010022837A CN101768326A CN 101768326 A CN101768326 A CN 101768326A CN 201010022837 A CN201010022837 A CN 201010022837A CN 201010022837 A CN201010022837 A CN 201010022837A CN 101768326 A CN101768326 A CN 101768326A
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Abstract
The invention discloses a preparation method of modified phenolic resin and an application thereof. The preparation method comprises the following steps of: firstly carrying out polycondensation on phenol, formaldehyde and urea under the conditions of a basic catalyst, the temperature of 85 to 95 DEG C and the pH value of 8 to 9, and regulating the pH value to 6.5 to 7.0 after the reaction is ended; then carrying out vacuum dehydration on polycondensation products under the vacuum condition, enabling the solid content to be 80 to 85 percent by weight, cooling to the room temperature, and regulating the viscosity to be 2.0 to 3.0Pa.s; and finally adding a surfactant and a foaming agent, stirring, discharging and packaging. Furthermore, a composite curing agent is also necessary to be mixed with the modified phenolic resin when in use according to the mass ratio of 100: 10 to 50. The prepared modified phenolic resin has the advantages of light weight, low toxicity, difficult combustion, low smoke, heat insulation, high temperature and low temperature resistance, and the like, can be widely used in the fields of building, transportation, shipping, chemical engineering, petroleum, and the like and has a certain social and economic benefits.
Description
Technical field
The present invention relates to modified foaming resol and solidifying agent production field, be specifically related to a kind of preparation and application thereof of modified phenolic resins.
Background technology
Present stage is used for mainly containing of external-wall heat-insulation material: polyurethane foam, polystyrene foam, phenolic resin foam etc., wherein have only polyurethane foam to can be used for spraying.And polyurethane foam, polystyrene foams etc. produce poisonous, obnoxious flavour owing to meet fire burning easily during burning, when fire failure takes place, cause casualties and the massive losses of property, thereby limited being extensive use of of they.Phenol foam is heat-resisting with it, difficult combustion, from put out, flame resistant penetrates, meet fire does not have advantage such as drippage and be subjected to extensive attention, but present stage can only be made sheet material, cause its cost to be higher than polystyrene foam, application is restricted, so developer and designing unit generally do not select this material for use.
The production of phenol formaldehyde foam at present mainly is to adopt expandable phenolic resin and whipping agent, solidifying agent, through mixing the casting foamable fast, its industrial characteristics are to need mould, and under 60 ℃～70 ℃ condition, generally, cause production efficiency low through solidifying more than 12 hours.And cost height, particularly some requirement of engineering site operations, adopt the foamable moulding, construction can't be finished.Particularly the exterior-wall heat insulation aspect can not adopt in-situ spraying as polyurethane foam, can only adopt the EPS board construction method, pastes on the wall with tackiness agent, and operating efficiency is low, and the cost height is pasted not strongly, and comes off easily.So be restricted aspect external wall outer insulation and the site operation.
If develop a kind of resol that sprays, make this product can site operation, will reduce its product cost greatly, have extensive market prospects.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of preparation method of modified phenolic resins, will mix use with composite curing agent according to the modified phenolic resins that this method makes, and makes it reach the requirement that the scene can spray, to solve the difficult problem of site operation.
The present invention also provide above-mentioned modified phenolic resins construct at the scene the spraying in application.
The preparation method of described modified phenolic resins, concrete steps are as follows:
Phenol, formaldehyde are metered in the reactor, stir down, transfer pH=8～9, be warming up to 85 ℃ with basic catalyst (20wt% sodium hydroxide solution).Controlled temperature reacted 2 hours at 85 ℃～95 ℃, and metering adds urea, polycondensation 1 hour.Transfer pH=6.5～7.0 with hydrochloric acid, vacuum hydro-extraction makes solid content to 80～85wt%, reduces to normal temperature, viscosimetric to 2.0～3.0Pas, and metering adds surfactivity, whipping agent, stirs blowing at a slow speed 10～20 minutes.Wherein, above-mentioned each proportion of raw materials and specification specifically see table 1.
Table 1
Described phenol is selected from phenol, cardanol, technical phenol; Wherein, the mass ratio of phenol and cardanol is 9: 1～2.5, and the mass ratio of technical phenol and cardanol is 9: 1～2.5.
Described tensio-active agent is a fatty alcohol-polyoxyethylene ether.
Described whipping agent is selected from Skellysolve A, iso-pentane, normal butane, methylene dichloride, chloroform, tetracol phenixin.
Modified phenolic resins according to above-mentioned preparation method obtains in use, further also need add composite curing agent, being about to prepared modified phenolic resins mixes by 100: 10～50 mass ratioes with composite curing agent, use double headed spray gun then, be sprayed onto and be coated with on the insulation object foaming.
Described composite curing agent is mineral acid and organic acid mixture, and wherein, mineral acid and organic acid mass ratio are 80～90: 10～20.
Described mineral acid is selected from phosphoric acid, hydrochloric acid, sulfuric acid; Described organic acid is selected from Phenylsulfonic acid, P-TOLUENE SULFO ACID 99, oxalic acid.
Use the modified phenolic resins material that the inventive method makes, have advantages such as lightweight, low toxicity, difficult combustion, low cigarette, heat insulation, high-low temperature resistant, cohesive force are strong, its performance test results is as shown in table 2 below.
Table 2
As can be seen from Table 2, the prepared modified phenolic resins of the present invention has excellent physicochemical property and heat-insulating property, little, the broad application temperature range of thermal conductivity, but under 150 ℃ of high temperature life-time service, under 200 ℃, obviously do not shrink yet.And the phenolic resin foam that the present invention makes also has good flame-retardant effect, oxygen index is higher, under flame directly acts on, have knot carbon, do not have drippage, do not have phenomenons such as curling, do not have thawing, its over-all properties is better than polyurethane foam, and cost is low, has a good application prospect, and can be used for the aspect such as chemical industry, oil, Highrise buildings, communications and transportation, aircraft industry, space field of easy presence of fire.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail.
Embodiment 1
1) preparation of modified phenolic resins:
With phenol 85g, cardanol 15g, formaldehyde (37wt%) 250g, add in three mouthfuls of beakers, transfer pH=8～9 with sodium hydroxide, stir and be warmed up to 85 ℃, 85～95 ℃ of controlled temperature, reacted 2 hours, add urea 10g again, reacted 1 hour, transfer pH=6.5～7.0 with hydrochloric acid, vacuum hydro-extraction, solid content reaches 85wt%.Reduce to normal temperature, viscosimetric adds fatty polyoxyethylenated alcohol 4g to 2.5Pas, and Skellysolve A 7g stirs 20 minutes blowings, packing.
2) preparation of composite curing agent:
With phosphatase 11 0g, sulfuric acid 80g, tosic acid 10g, put into there-necked flask, stirred 20 minutes, treat that tosic acid all dissolves blowing, the packing.
Get the 100g modified phenolic resins, the 12g composite curing agent mixes, and spraying gets final product.
Embodiment 2
1) preparation of modified phenolic resins:
With technical phenol 90g, cardanol 10g, formaldehyde (37wt%) 200g, add in the there-necked flask, stir with sodium hydroxide bar pH=8～9 and be warmed up to 85 ℃.85 ℃～95 ℃ of controlled temperature reacted 2 hours, added urea 8g again, reacted 1 hour, transferred pH=6.5～7 with hydrochloric acid, vacuum hydro-extraction, and solid content reaches 85wt%, reduces to normal temperature, and viscosimetric 3Pas adds fatty polyoxyethylenated alcohol 6g, iso-pentane 10g, the blowing packing.
2) preparation of composite curing agent:
Phosphatase 11 0g, hydrochloric acid 200g, Phenylsulfonic acid 10g are put into there-necked flask, stirred 20 minutes, treat that Phenylsulfonic acid all dissolves, the blowing packing.
Get the 100g modified phenolic resins, the 40g composite curing agent mixes, the spraying interface.
Embodiment 3
1) preparation of modified phenolic resins:
With phenol 80g, cardanol 20g, formaldehyde (37wt%) 200g, add in the there-necked flask, stir with sodium hydroxide pH=8～9 and be warmed up to 85 ℃.85 ℃～95 ℃ of controlled temperature reacted 2 hours, added urea 60g reaction 1 hour again.Transfer pH=6.5～7 with hydrochloric acid, vacuum hydro-extraction, solid content reaches 85wt%, reduces to normal temperature, and viscosimetric adds fatty polyoxyethylenated alcohol 5g, ethylene dichloride 6g to 2.8Pas, the blowing packing.
2) preparation of composite curing agent:
Phosphatase 11 0g, sulfuric acid 90g, oxalic acid 5g are put into there-necked flask, stirred 20 minutes, treat that oxalic acid all dissolves, the blowing packing.
Get the 100g modified phenolic resins, the 15g composite curing agent mixes, and spraying gets final product.
Embodiment 4
1) preparation of modified phenolic resins:
With technical phenol 85g, cardanol 16g, formaldehyde (37wt%) 180g, add in the there-necked flask, stir with sodium hydroxide pH=8～9 and be warmed up to 85 ℃.85 ℃～95 ℃ of controlled temperature reacted 2 hours, added urea 10g reaction 1 hour again.Transfer pH=6.5～7 with hydrochloric acid, vacuum hydro-extraction, solid content reaches 85wt%, reduces to normal temperature, and viscosimetric adds fatty polyoxyethylenated alcohol 5g, chloroform 10g to 2.5Pas, the blowing packing.
2) preparation of composite curing agent:
With phosphatase 11 5g, sulfuric acid 85g, tosic acid 10g, put into there-necked flask and mixed 20 minutes, treat that tosic acid all dissolves, the blowing packing.
Get the 100g modified phenolic resins, the 13g composite curing agent mixes, and spraying gets final product.
Embodiment 5
1) preparation of modified phenolic resins:
With phenol 83g, cardanol 17g, formaldehyde (37wt%) 205g, add in the there-necked flask, stir with sodium hydroxide pH=8～9 and be warmed up to 85 ℃.85 ℃～95 ℃ of controlled temperature reacted 2 hours, added urea 9g reaction 1 hour again.Transfer pH=6.5～7 with hydrochloric acid, vacuum hydro-extraction, solid content reaches 83wt%, reduces to normal temperature, and viscosimetric adds fatty polyoxyethylenated alcohol 6g, tetracol phenixin 8g to 3Pas, stirs the blowing packing 20 minutes.
2) preparation of composite curing agent:
With phosphoric acid 8g, sulfuric acid 75g, tosic acid 7g, put into there-necked flask and mix, treat that tosic acid all dissolves, the blowing packing.
Get the 100g modified phenolic resins, the 10g composite curing agent mixes, and spraying gets final product.
Should be noted that at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement the technical scheme of invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (10)
1. the preparation method of a modified phenolic resins is characterized in that, may further comprise the steps:
At first, phenol, formaldehyde, urea are transferred pH to 6.5～7.0 in basic catalyst, 85～95 ℃, pH=8～9 time generation polycondensation after reaction finishes;
Then, under vacuum condition,, make its solid content to 80～85wt%, reduce to normal temperature, regulate viscosity to 2.0～3.0Pas above-mentioned polycondensation product vacuum hydro-extraction;
At last, add tensio-active agent and whipping agent, stirring, blowing, packing.
2. preparation method according to claim 1 is characterized in that described phenol is selected from phenol, cardanol, technical phenol; Wherein, the mass ratio of phenol and cardanol is 9: 1～2.5, and the mass ratio of technical phenol and cardanol is 9: 1～2.5.
3. preparation method according to claim 1 is characterized in that, the mass ratio of described phenol and formaldehyde is 100: 160～250, and the mass ratio of phenol and urea is 100: 6～10.
4. preparation method according to claim 1 is characterized in that, described basic catalyst is a sodium hydroxide solution.
5. preparation method according to claim 1 is characterized in that, described tensio-active agent is a fatty alcohol-polyoxyethylene ether, and the mass ratio of itself and phenol is 3～5: 100.
6. preparation method according to claim 1 is characterized in that described whipping agent is selected from Skellysolve A, iso-pentane, normal butane, methylene dichloride, chloroform, tetracol phenixin, and the mass ratio of whipping agent and phenol is 6～10: 100.
7. the application during the prepared modified phenolic resins of claim 1 sprays at the scene, it is characterized in that, further, also need add composite curing agent in use, being about to the prepared modified phenolic resins of claim 1 mixes by 100: 10～50 mass ratioes with composite curing agent, use double headed spray gun then, be sprayed onto and be coated with on the insulation object foaming.
8. application according to claim 7 is characterized in that, described composite curing agent is mineral acid and organic acid mixture, and wherein, mineral acid and organic acid mass ratio are 80～90: 10～20.
9. application according to claim 8 is characterized in that described mineral acid is selected from phosphoric acid, hydrochloric acid, sulfuric acid.
10. application according to claim 8 is characterized in that described organic acid is selected from Phenylsulfonic acid, P-TOLUENE SULFO ACID 99, oxalic acid.
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| CN2010100228378A CN101768326B (en) | 2010-01-15 | 2010-01-15 | Preparation method of modified phenolic resin and application thereof |
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| CN2010100228378A CN101768326B (en) | 2010-01-15 | 2010-01-15 | Preparation method of modified phenolic resin and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250445A (en) * | 2011-06-07 | 2011-11-23 | 中国林业科学研究院林产化学工业研究所 | Method for preparing phenolic foamed plastic |
| CN102504153A (en) * | 2011-11-09 | 2012-06-20 | 长春工业大学 | Method for preparing foaming phenolic formaldehyde resin |
| CN102977547A (en) * | 2012-10-08 | 2013-03-20 | 山东莱芜润达新材料有限公司 | Low temperature rapid-foaming phenol formaldehyde foam thermal insulation board preparation method |
| CN103224689A (en) * | 2013-05-09 | 2013-07-31 | 山西新举节能建材科技有限公司 | Fireproof thermal insulation modified phenolic plate and making method thereof |
| CN105175664A (en) * | 2015-11-05 | 2015-12-23 | 北京莱恩斯高新技术有限公司 | Phenolic-resin-type surfactant for phenolic foam plastic and preparation method thereof |
| CN106496470A (en) * | 2016-09-21 | 2017-03-15 | 沈阳化工大学 | A kind of phenol formaldehyde foam of 3 nitro, 4 hydroxyethylaminophenol formaldehyde and preparation method thereof |
| CN111205799A (en) * | 2020-02-28 | 2020-05-29 | 杭摩新材料(嘉兴)有限公司 | Production process of cardanol modified phenolic resin adhesive |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065077A (en) * | 1992-04-10 | 1992-10-07 | 沈阳化工学院 | Modified phenolic foam |
| CN101148515B (en) * | 2007-09-12 | 2010-06-02 | 北京莱恩斯高新技术有限公司 | Composite pnenolic aldehyde foam heat-insulating board for building and forming method thereof |
-
2010
- 2010-01-15 CN CN2010100228378A patent/CN101768326B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250445A (en) * | 2011-06-07 | 2011-11-23 | 中国林业科学研究院林产化学工业研究所 | Method for preparing phenolic foamed plastic |
| CN102504153A (en) * | 2011-11-09 | 2012-06-20 | 长春工业大学 | Method for preparing foaming phenolic formaldehyde resin |
| CN102977547A (en) * | 2012-10-08 | 2013-03-20 | 山东莱芜润达新材料有限公司 | Low temperature rapid-foaming phenol formaldehyde foam thermal insulation board preparation method |
| CN103224689A (en) * | 2013-05-09 | 2013-07-31 | 山西新举节能建材科技有限公司 | Fireproof thermal insulation modified phenolic plate and making method thereof |
| CN105175664A (en) * | 2015-11-05 | 2015-12-23 | 北京莱恩斯高新技术有限公司 | Phenolic-resin-type surfactant for phenolic foam plastic and preparation method thereof |
| CN106496470A (en) * | 2016-09-21 | 2017-03-15 | 沈阳化工大学 | A kind of phenol formaldehyde foam of 3 nitro, 4 hydroxyethylaminophenol formaldehyde and preparation method thereof |
| CN106496470B (en) * | 2016-09-21 | 2018-08-07 | 沈阳化工大学 | A kind of phenol formaldehyde foam and preparation method thereof of 3- nitros -4- hydroxyethylaminophenol formaldehyde |
| CN111205799A (en) * | 2020-02-28 | 2020-05-29 | 杭摩新材料(嘉兴)有限公司 | Production process of cardanol modified phenolic resin adhesive |
| CN111205799B (en) * | 2020-02-28 | 2021-01-19 | 杭摩新材料(嘉兴)有限公司 | Production process of cardanol modified phenolic resin adhesive |
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