CN101717514B - Modified phenolic resin, foamed material thereof and method for preparing same - Google Patents
Modified phenolic resin, foamed material thereof and method for preparing same Download PDFInfo
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- CN101717514B CN101717514B CN2009102322193A CN200910232219A CN101717514B CN 101717514 B CN101717514 B CN 101717514B CN 2009102322193 A CN2009102322193 A CN 2009102322193A CN 200910232219 A CN200910232219 A CN 200910232219A CN 101717514 B CN101717514 B CN 101717514B
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Abstract
The invention relates to a modified phenolic resin, a foamed material thereof and a method for preparing the same, and belongs to the technical field of polymeric building energy-saving materials. The modified phenolic resin comprises the following components in part by weight: 100 parts of phenol, 30 to 100 parts of paraformaldehyde, 0.2 to 5 parts of catalytic agent, 5 to 30 parts of amino terminated polyether polymer and 1 to 8 parts of performance additive. The modified phenolic resin is prepared through the steps of low temperature addition and high temperature polycondensation. The foamed material of the modified phenolic resin is prepared through the steps of: mixing the modified phenolic resin, a foam stabilizer, a foaming agent and a foaming and nucleating auxiliary agent, and then pre-heating the mixture; adding a curing agent and raising the temperature to prefoam the mixture; and finally raising the temperature to cure the mixture. Compared with the prior art, the foamed material has the advantages of high closed porosity, simple process, environmental protection, high safety and the like.
Description
Technical field
The present invention relates to a kind of modified phenolic resins, and a kind of modified phenolic resins foam materials, also relate to its preparation method simultaneously, belong to polymer energy-saving building materials technical field.
Background technology
Phenol foam is because its light weight, raw material are easy to get, the flame retardant resistance height, meet characteristics such as naked light surface carbonization, smoke density be low, be subjected to increasing attention, especially building energy conservation aspect, phenol foam is widely used in external wall outer insulation, brings the revolution of energy-saving building technology and product.But phenol foam is because itself structure, makes it have weak points such as fragility is big, easily dry linting, ultimate compression strength be low, directly limited the use range of phenol foam.
In recent years, phenol foam is carried out modification is the focus of studying in the industry always.Chinese patent CN200310113965.3 adopts modified additive that resol is carried out modification, CN200710201512.4 has adopted polyurethane(s) as properties-correcting agent resol to be carried out modification, U.S. Pat 647244 is mainly carried out modification by foam process and auxiliary agent, obtains the modified phenolic resins foam.Above technology is lower to the foam rate of closed hole of phenol foam, and the water-intake rate height not directly is used for external wall outer insulation, so modified effect is all not ideal enough.
Summary of the invention
The objective of the invention is weak point at above-mentioned prior art existence, propose a kind of ultimate compression strength height, be difficult for the dry linting modified phenolic resins, be used to prepare the modified phenolic resins foam materials that water-intake rate is low, can be directly used in external wall outer insulation, provide its preparation method simultaneously.
Purpose of the present invention is achieved through the following technical solutions: a kind of modified phenolic resins, make by the component of following weight part:
100 parts of phenol
Paraformaldehyde 96 30-100 part
Catalyzer 0.2-5 part
Amino Terminated polyether(ATPE) base polymer 5-30 part
Modified additive 1-8 part
The preparation method of above-mentioned modified phenolic resins may further comprise the steps:
The first step, low temperature addition---with phenol and catalyst mix, in 30-50 ℃ of following 30-90 minute, divide 2-6 even amount to add Paraformaldehyde 96, add back insulation 10-30 minute at every turn;
Second step, high-temperature polycondensation---be warming up to 60-90 ℃, be incubated 10-60 minute, be cooled to 30-50 ℃ again after, add the Amino Terminated polyether(ATPE) base polymer, be incubated after 10-30 minute, add modified additive, be incubated 10-30 minute, reduce to room temperature, the adjusting pH value is neutrality extremely; Control method commonly used transfers to 7-8 for dripping anhydrous acetic acid with pH value, promptly makes modified phenolic resins of the present invention.
Above-mentioned modified phenolic resins is owing to make at phenol and formaldehyde reaction polycondensation phase adding Amino Terminated polyether(ATPE) base polymer, make polyether structure by amido and methylol reactive grafting in the resol structure, therefore fundamentally improved the fragility of resol, make it to have the high compression strength height, be difficult for dry linting.
Amino Terminated polyether(ATPE) base polymer preferably, its relative molecular mass is 500-10000, by primary amino or secondary amino group in polyethers polymkeric substance two ends sealed.
Modified phenolic resins foam materials of the present invention is made by the component of following weight part:
100 parts of modified phenolic resinss
Foam stabilizer 1-8 part
Whipping agent 5-25 part
Foaming nucleation auxiliary agent 0.1-5 part
Solidifying agent 8-30 part
Preparation method's step of above-mentioned modified phenolic resins foam materials is: behind modified phenolic resins, foam stabilizer, whipping agent, foaming nucleation auxiliary agent uniform mixing, be preheated to 20-60 ℃ (preferably being preheated to 45-60 ℃), add solidifying agent 8-30, stirred 1-10 minute, be warming up to 60-80 ℃ of pre-frothing, in 2-20 minute, slowly be warming up to 80-100 ℃ again, slaking 8-25 minute, obtain modified phenolic resins foam materials of the present invention.
Above-mentioned foaming nucleation auxiliary agent helps bubble nucleating, therefore can make phenolic resin foam evenly fine and smooth, preferred modified Nano particle preferably selects modified manometer silicon dioxide, nano titanium oxide, nano-calcium carbonate etc. during use, and particle size range is advisable for the 2-500 nanometer.The modified Nano particle is by coupling agent modified, make nanoparticle before unmodified, be uniformly dispersed, have very strong affinity with resol, coupling agent is selected from silane coupling agent KH550, KH560, KH570, titanate coupling agent ND-9401, TC-3, TC-AT etc.;
Compared with prior art, the foam materials that obtains of the present invention has following advantage:
1, the rate of closed hole height: the present invention adopts long chain polymer as resin flexible main provider, its crosslinked segment is longer, can guarantee intermolecular enough rotations, gained foam toughness can access effective improvement, the dry linting rate is extremely low, in this simultaneously, higher molecular bond energy and suitable viscosity help the raising of phenolic resin foam rate of closed hole between Amino Terminated polyether(ATPE) two ends amido and the methylol, in this simultaneously, cooperate the adjustment of relevant foam process, adopt sectional temperature-controlled mode, help the coupling of whipping agent and solidifying agent and resin solidification speed more, obtain the high foam materials of rate of closed hole, (the modified phenolic resins foam materials rate of closed hole that obtains can reach 98% for the water tolerance of raising foam materials and heat retaining property, water-intake rate reaches 2.05%, and thermal conductivity reaches 0.022 (W/mk), and vertical panel face tensile strength reaches 0.13Mpa).
2, technology is simple: the flow process of foam process adopts sectional temperature-controlled, and is simple, easy to operate in actual production process, can effectively raise production efficiency, and investment in fixed assets is lower, thereby has reduced the manufacturing cost of modified phenolic resins foam materials.
3, Environmental Safety height: the modified phenolic resins foam materials does not have waste water, pollution-free from the production of modified phenolic resins to foaming process, and especially foaming process adopts the floride-free whipping agent of alkanes, and is environmentally friendly, no global greenhouse effect coefficient.
Embodiment
The invention will be further described below in conjunction with specific examples.
Embodiment 1
In 1 ton of reactor, add 400kg phenol and as the 3kg caustic soda aqueous solution of catalyzer, 35 ℃ were stirred 20 minutes, 150kg Paraformaldehyde 96 even in three batches amount in 60 minutes adds in the reactor, add the back insulation 15 minutes that finishes, be warming up to 75 ℃, be incubated 30 minutes, be cooled to 30 ℃, add 20kg Amino Terminated polyether(ATPE) (relative molecular mass 5000), be incubated 20 minutes, adding is as the 5kg butanediamine of modified additive, be incubated 10 minutes, reduce to room temperature, drip anhydrous acetic acid, pH value is transferred to neutrality, obtain modified phenolic resins.
Then, with modified phenolic resins (relative molecular mass 5000) 100kg that obtains, add the compound foam stabilizer (sodium lauryl sulphate of 2kg, silicone surfactant, mass ratio is 1: 0.5), 8kg combined foaming agent (Skellysolve A, normal hexane, mass ratio is 1: 1), 4kg foaming nucleation auxiliary agent KH570 modified nano calcium carbonate, even in 25 ℃ of following vigorous stirring, add 10kg solidifying agent (phosphoric acid, tosic acid, mass ratio is 1: 1), stirred 2 minutes, put into 60 ℃ of environment pre-frothing, blowing temperature slowly was warming up to 80 ℃ in 5 minutes, slaking 20 minutes obtains modified phenolic resins foam A, and its The performance test results is seen Table 1.
Embodiment 2
In 1 ton of reactor, add 400kg phenol, 4kg caustic soda and calcium hydroxide mixed aqueous solution, 45 ℃ were stirred 20 minutes, the 280kg Paraformaldehyde 96 added in 40 minutes in the reactor in four batches, added the back insulation 20 minutes that finishes, and added the caustic soda aqueous solution of 1kg, be warming up to 80 ℃, be incubated 40 minutes, be cooled to 40 ℃, add 50kg Amino Terminated polyether(ATPE) (relative molecular mass 2000), be incubated 20 minutes, add the 4kg pentamethylene diamine, be incubated 20 minutes, reduce to room temperature, regulate the pH value to neutral.
Then, with above-mentioned Amino Terminated polyether(ATPE) (relative molecular mass 2000) modified phenolic resins 100kg, add the compound foam stabilizer of 1kg and (comprise Sodium dodecylbenzene sulfonate, silicone surfactant, mass ratio is 1: 1), the 8kg combined foaming agent (comprises Skellysolve A, hexanaphthene, mass ratio is 1: 0.5), 5kg foaming nucleation auxiliary agent KH550 modified manometer silicon dioxide, even in 25 ℃ of following vigorous stirring, add the 15kg solidifying agent and (comprise phosphoric acid, tosic acid, mass ratio is 1: 0.5), stirred 3 minutes, put into 65 ℃ of environment pre-frothing, blowing temperature slowly was warming up to 85 ℃ in 10 minutes, slaking 25 minutes obtains modified phenolic resins foam B, and its The performance test results is seen Table 1.
Embodiment 3
In 1 ton of reactor, add 400kg phenol, 10kg caustic soda and calcium oxide mixed aqueous solution, 50 ℃ were stirred 15 minutes, the 350kg Paraformaldehyde 96 was all measured in five batches at 90 minutes and is added in the reactor, add the back insulation 30 minutes that finishes, add the caustic soda aqueous solution of 3kg, be warming up to 75 ℃, be incubated 30 minutes, be cooled to 35 ℃, add 100kg Amino Terminated polyether(ATPE) (relative molecular mass 8000), be incubated 30 minutes, add the 6kg butanediamine, be incubated 20 minutes, reduce to room temperature, regulate the pH value, obtain modified phenolic resins to neutral.
Then with Amino Terminated polyether(ATPE) (relative molecular mass 8000) modified phenolic resins 100kg, add the compound foam stabilizer of 6kg and (comprise sodium cetanesulfonate, silicone surfactant, mass ratio is 1: 2), the 12kg combined foaming agent (comprises sherwood oil, hexanaphthene, mass ratio is 1: 2), 0.5kg foaming nucleation auxiliary agent TC-3 modified nano-titanium dioxide, even in 45 ℃ of following vigorous stirring, add the 20kg solidifying agent and (comprise phosphoric acid, tosic acid, mass ratio is 1: 2), stirred 3 minutes, put into 70 ℃ of environment pre-frothing, blowing temperature slowly was warming up to 90 ℃ in 10 minutes, slaking 15 minutes, obtain modified phenolic resins foam C, its The performance test results is seen Table 1.Get common phenol formaldehyde foam D and carry out performance test, the results are shown in Table 1.
Table 1
| Numbering | Rate of closed hole (%) | Water-intake rate (%) | Thermal conductivity (W/mk) | Vertical panel face tensile strength (MPa) |
| A | 98 | 2.05 | 0.022 | 0.13 |
| B | 98 | 2.11 | 0.022 | 0.13 |
| C | 98 | 2.09 | 0.023 | 0.12 |
| D | 76 | 9.8 | 0.107 | 0.033 |
This shows, amine terminated polyether polymer modification phenol formaldehyde foam various aspects of performance index of the present invention all obviously is better than existing common phenol formaldehyde foam, especially rate of closed hole and water-intake rate, and heat-insulating property also significantly improves, therefore can better application in external wall outer insulation.
Claims (9)
1. modified phenolic resins, make by the component of following weight part:
Described modified additive is butanediamine or pentamethylene diamine.
2. modified phenolic resins according to claim 1 is characterized in that: described amine terminated polyether polymkeric substance relative molecular mass is 500-10000, by primary amino or secondary amino group in polyethers polymkeric substance two ends sealed.
3. modified phenolic resins according to claim 2 is characterized in that: described catalyzer is the caustic soda aqueous solution or caustic soda and calcium hydroxide mixed aqueous solution.
4. according to the preparation method of claim 1 or 3 described modified phenolic resinss, it is characterized in that may further comprise the steps:
The first step, low temperature addition---with phenol and catalyst mix, in 30-50 ℃ of following 30-90 minute, divide 2-6 even amount to add Paraformaldehyde 96, add back insulation 10-30 minute at every turn;
Second step, high-temperature polycondensation---be warming up to 60-90 ℃, be incubated 10-60 minute, be cooled to 30-50 ℃ again after, adding Amino Terminated polyether(ATPE) base polymer, be incubated after 10-30 minute, add modified additive, be incubated 10-30 minute, reduce to room temperature, regulate the pH value, make modified phenolic resins to neutral.
5. according to the foam materials of the described modified phenolic resins of claim 4, make by the component of following weight part:
6. foam materials according to claim 5 is characterized in that: described foaming nucleation auxiliary agent is the modified Nano particle.
7. foam materials according to claim 6 is characterized in that: described modified Nano particle is one of nano silicon, nano titanium oxide, nano-calcium carbonate, and particle size range is the 2-500 nanometer.
8. foam materials according to claim 6 is characterized in that: described foam stabilizer adopts sodium lauryl sulphate and the silicone surfactant of mass ratio 1: 0.5-2; It is 1 that described whipping agent adopts mass ratio: the Skellysolve A of 0.5-2 and normal hexane, and perhaps adopting mass ratio is 1: the sherwood oil of 0.5-2 and hexanaphthene; It is 1 that described solidifying agent adopts mass ratio: the phosphoric acid of 0.5-2 and tosic acid.
9. the preparation method of foam materials according to claim 5, it is characterized in that step is: behind modified phenolic resins, foam stabilizer, whipping agent, foaming nucleation auxiliary agent uniform mixing, be preheated to 20-60 ℃, add solidifying agent 8-30 part, stirred 1-10 minute, and be warming up to 60-80 ℃ of pre-frothing, in 2-20 minute, slowly be warming up to 80-100 ℃ again, slaking 8-25 minute, obtain the modified phenolic resins foam materials.
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| CN102731961B (en) * | 2011-10-18 | 2014-03-19 | 蓝云飞 | Phenolic foam composite insulation material and production method thereof |
| CN102886906B (en) * | 2011-11-17 | 2015-08-05 | 济南圣泉集团股份有限公司 | A kind of ageing method of phenolic foam material and curing equipment thereof |
| CN103254378A (en) * | 2013-05-08 | 2013-08-21 | 苏州美克思科技发展有限公司 | Modified carbon foam phenolic resin and preparation method thereof |
| CN103224689B (en) * | 2013-05-09 | 2015-03-11 | 山西新举节能建材科技有限公司 | Fireproof thermal insulation modified phenolic plate and making method thereof |
| CN104072941B (en) * | 2014-07-18 | 2016-04-06 | 锦州市好为尔保温材料有限公司 | A kind of nano modification phenolic foam heat insulation plate and preparation method thereof |
| CN104909755A (en) * | 2015-06-04 | 2015-09-16 | 合肥和安机械制造有限公司 | Composite modified bauxite-carbonized foamed phenolic resin-based thermal insulation material for forklift engine exhaust pipe and preparation method of thermal insulation material |
| CN105111674A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Ionic liquid improved low-acidity and high-activity phenolic resin curing agent |
| CN107141713A (en) * | 2017-07-06 | 2017-09-08 | 湖南中野高科技特种材料有限公司 | A kind of method for producing high-performance pnenolic aldehyde foam |
| CN108424610A (en) * | 2018-04-23 | 2018-08-21 | 石磊 | A kind of preparation method of flexible Anti-pressure phenolic foam |
| CN110194849A (en) * | 2019-06-26 | 2019-09-03 | 成都玉龙化工有限公司 | A kind of production technology of novel melamine foam |
| CN111483105B (en) * | 2020-04-23 | 2021-09-24 | 合肥荣丰包装制品有限公司 | EPS foam material forming device and process |
| CN113388098B (en) * | 2021-06-11 | 2024-02-27 | 北京化工大学常州先进材料研究院 | Preparation method of special foaming resin for polyether modified polyester |
| CN114525025B (en) * | 2021-09-23 | 2023-08-15 | 山东联欣环保科技有限公司 | Copolymer foam material and preparation method and application thereof |
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