CN105694357B - The preparation method of polyether-modified biomass resin foamed rapidly at normal temperature - Google Patents
The preparation method of polyether-modified biomass resin foamed rapidly at normal temperature Download PDFInfo
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- CN105694357B CN105694357B CN201610046531.3A CN201610046531A CN105694357B CN 105694357 B CN105694357 B CN 105694357B CN 201610046531 A CN201610046531 A CN 201610046531A CN 105694357 B CN105694357 B CN 105694357B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
Abstract
The invention discloses a kind of preparation method of polyether-modified biomass resin foamed rapidly at normal temperature, comprise the following steps：After PPG and more biomass liquefying resins in mass ratio 1: 51: 20 are mixed, under the conditions of temperature is 30 40 DEG C, stir, regulation pH value is 9 10；By mass, weigh the modified biomass liquefied resin obtained by 100 parts of step S1, add 8 12 parts of surfactants, 20 30 parts of curing agent, 5 10 parts of foaming agents, 50 60 parts of isocyanates, compound stirs, mould or cast in situs, the curing molding under normal temperature condition are injected, obtains polyether-modified biomass resin foamed material.The present invention is modified by industrializing PPG to biomass liquefying resin, and the fast foaming shaping of biomass liquefying resin is realized under normal temperature condition, cost of manufacture and cycle is reduced, can also increase the intensity and toughness of biomass resin foamed material.
Description
Technical field
The present invention relates to field of material preparation, and in particular to a kind of system of polyether-modified biomass resin foamed rapidly at normal temperature
Preparation Method.
Background technology
Expandable resin is prepared using biological material, is one of effective way of the high-valued application of biological material, it is raw
The material of the resin expanded preparation of material has light, heat-insulated, sound insulation, damping, fire-retardant, reusable edible and can biomass degradation etc.
Premium properties, petroleum base polymeric foamed material can be substituted and be widely used in the fields such as building, traffic.But biomass resin
Expanded material is there is also some shortcomings during preparation and utilization, for example resin activity is relatively low, blowing temperature is too high, material system
Standby cycle length etc., is restricted its popularization and application.At present, biomass liquefying resin-made preparation foam material reaction temperature is utilized
Typically more than 70 DEG C, manufacturing cycle is at least 30min, or even 120min.As Liu Le group with bamboo liquefied product resin prepare
Expanded material needs thermalization 3-5 hours in 70-90 degrees Celsius of baking oven to be again stripped completion.Zhang Wenbo is prepared with wooden liquefied substance
Expanded material needs to be placed in 40-60 degrees Celsius of baking oven the 30-50min that foams, and solidifies 1- in 80-100 degrees Celsius of baking oven is placed in
1.5h could prepare completion.Zhang Jinping prepares phenolic foam using bamboo liquefied product and need to foamed under the conditions of 60-80 DEG C
Just it is molded after 2h.Sun Fengwen natural fiber biological materials prepare biomass-based foamed material need to be in 60-90 DEG C of environment
Biomass-based foamed material can be just made in foamed solidification 60-180min.
At present, using biomass resin foamed material, there is also some shortcomings, such as resin during preparation and utilization
Activity is relatively low, blowing temperature is too high, material long preparation period etc..
The content of the invention
To solve the above problems, the invention provides a kind of preparation side of polyether-modified biomass resin foamed rapidly at normal temperature
Method, by adding industrialization PPG in proportion, biomass liquefying resin is modified, realized under normal temperature condition
The fast foaming shaping of biomass liquefying resin, reduces cost of manufacture and cycle, can also increase the resin expanded material of biomass
The intensity and toughness of material.
To achieve the above object, the technical scheme taken of the present invention is：
The preparation method of polyether-modified biomass resin foamed rapidly at normal temperature, comprises the following steps：
S1, biomass liquefying resin modified：
It it is 30-40 DEG C in temperature after PPG and more biomass liquefying resins in mass ratio 1: 5-1: 20 are mixed
Under the conditions of, stir, regulation pH value is 9-10；
S2, biomass are resin expanded：
By mass, the modified biomass liquefied resin obtained by 100 parts of step S1 is weighed, adds 8-12 part surface-actives
Agent, 20-30 part curing agent, 5-10 part foaming agents, 50-60 part isocyanates, compound stir, and inject mould or scene is poured
Build, the curing molding under the conditions of normal temperature (25 DEG C), obtain polyether-modified biomass resin foamed material.
Wherein, the biomass liquefying resin is prepared by following steps：
It is right by the use of hydrochloric acid or sulfuric acid as catalyst using the mixture of phenol or phenol and polyethylene glycol as liquefier
The biological material of the mesh of 40 mesh -100 is liquefied, such as：Timber, bamboo wood, stalk or cornstalk etc., then in the basic conditions,
The biomass liquefying resin of formaldehyde or paraformaldehyde synthesis expandability is added, wherein, the mass ratio of phenol and PEG-4000
For 100: 0-50: 50.
Wherein, the surfactant is Tween-80, OP-10, one kind of castor oil nonionic surface active agent or two
The mixture of the kind above.
Wherein, the curing agent is phosphoric acid, one or several kinds of mixtures of p-methyl benzenesulfonic acid.
Wherein, the foaming agent is pentane, isopentane, one or more of mixtures of petroleum ether.
Wherein, the isocyanates is NPU-MR200, ten thousand magnificent PM200, BASF M20S, Bayer 44V20L, Hensel step
One kind in 5005.
Wherein, the PPG is polyethers 3628, polyethers 330, polyethers 4110, one kind in polyethers DL400 or several
The mixture of kind.
Wherein, biomass liquefying resin can also use number of patent application：201210047140.5、20141060186.7、
201110418128.6, the preparation method of biomass liquefying resin in 200910217110.2 is prepared.
The invention has the advantages that：
1) biomass resin is modified by the method for physical blending, can in the case where controlling pH value and temperature conditionss
To prepare modified biomass resin, the expanded material intensity and toughness of preparation are improved, and operating process is simple and practical, is easy to work
Industry.
2) preparation technology simple possible, preparation time is short, prepares environmental condition and requires low, goes for cast in situs hair
Bubble.
3) polyethers, surfactant, curing agent, foaming agent, the isocyanates used is commercially available, and material source is wide.It is right
After biomass liquefying resin is modified, the expanded material of preparation improves than pure biomass liquefying expanded material internal bond strength
35%, compressive strength 50%, thermal conductivity factor is 0.03-0.06W/ (mk), and the production cycle can foreshorten to 10min or so.
4) polyether-modified biomass resin cast in situs expanded material is used, it is multiple that large format dividing plate and casing etc. can be prepared
Condensation material.Expanded material core density can be reduced to 0.07gcm-1 or so, improve biomass resin foamed material application
Scope.
Embodiment
In order that objects and advantages of the present invention are more clearly understood, the present invention is carried out with reference to embodiments further
Describe in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit this hair
It is bright.
The biomass liquefying resin used in following examples is made by oneself for laboratory, and viscosity is 1000-1500mPS (25
DEG C), solid content 50-55%, pH value is 10-11 or so.
Embodiment 1
S11, biomass liquefying resin modified.PPG 330 is added into more biomass liquefying resins, is in temperature
Under the conditions of 30-40 DEG C, stir, regulation pH value is 9.5, adding proportion biomass liquefying resin：PPG is
10∶1。
S12, biomass are resin expanded.In mass, 100 parts of modified biomass liquefied resins are weighed, add 10 parts of surfaces
Activating agent (Tween-80: OP-10=1: 1), 20 parts of curing agent (phosphoric acid: p-methyl benzenesulfonic acid=3: 1), 5 parts of foaming agents (positive penta
Alkane), 55 parts of isocyanates (PM200).Compound is stirred, injects in mould, is solidified under the conditions of normal temperature (25 DEG C)
Type, obtain polyether-modified biomass resin foamed material.
S13, polyether-modified biomass resin foamed material is prepared using the method for molding, the production cycle can for 10min/ times
For producing high-strength light pavement.
S14, foaming material performance：Density 0.10gcm-1, compressive strength 0.35MPa, thermal conductivity factor 0.034-0.45W/
(mk), oxygen index (OI) 40%.
Embodiment 2
S21, biomass liquefying resin modified.PPG 4110 is added into more biomass liquefying resins, is in temperature
Under the conditions of 30-40 DEG C, stir, regulation pH value is 9.0, and adding proportion biomass liquefying portions of resin PPG is
15∶1。
S22, biomass are resin expanded.In mass, 100 parts of modified biomass liquefied resins are weighed, add 12 parts of surfaces
Activating agent (Tween-80: OP-10=1: 1), 18 parts of curing agent (phosphoric acid: p-methyl benzenesulfonic acid=3: 1), 5 parts of foaming agents (positive penta
Alkane), 50 parts of isocyanates (PM200).Compound is stirred, injects in mould, is solidified under the conditions of normal temperature (25 DEG C)
Type, obtain polyether-modified biomass resin foamed material.
S23, polyether-modified biomass resin foamed material is prepared using the method for molding, the production cycle is 10min/ times.
It can be used for producing high-strength light pavement.
S24, foaming material performance: density 0.11gcm-1, compressive strength 0.30MPa, thermal conductivity factor 0.040-0.48W/
(mk), oxygen index (OI) 38%.
Embodiment 3
S31, biomass liquefying resin modified.PPG 330 is added into more biomass liquefying resins, is in temperature
Under the conditions of 30-40 DEG C, stir, regulation pH value is 10, and adding proportion biomass liquefying portions of resin PPG is 8:
1。
S32, biomass are resin expanded.In mass, 100 parts of modified biomass liquefied resins are weighed, 8 parts of surfaces is added and lives
Property agent (Tween-80: OP-10=1: 1), 25 parts of curing agent (phosphoric acid: p-methyl benzenesulfonic acid=3: 1), 5 parts of foaming agents (petroleum ether),
60 parts of isocyanates (NPU-MR200).Compound is stirred, cast in situs, the curing molding under the conditions of normal temperature (25 DEG C),
Obtain polyether-modified biomass resin foamed material.
S33, polyether-modified biomass resin foamed material, material solidification assembly time prepared using the method for cast in situs
About 5-15min.It can be used for large format dividing plate and compartment casing.
S34, foaming material performance：Density 0.07gcm-1, compressive strength 0.25MPa, thermal conductivity factor 0.050-
0.060W/ (mk), oxygen index (OI) 35%.
Embodiment 4
S41, biomass liquefying resin modified.PPG 3628 is added into more biomass liquefying resins, is in temperature
Under the conditions of 30-40 DEG C, stir, regulation pH value is 9.5, adding proportion biomass liquefying resin：PPG is
15∶1。
S42, biomass are resin expanded.In mass, 100 parts of modified biomass liquefied resins are weighed, add 12 parts of surfaces
Activating agent (Tween-80: OP-10=1: 1), 20 parts of curing agent (phosphoric acid: p-methyl benzenesulfonic acid=3: 1), 8 parts of foaming agents (positive penta
Alkane), 50 parts of isocyanates (Bayer 44V20L).Compound is stirred, cast in situs, solidified under the conditions of normal temperature (25 DEG C)
Shaping, obtains polyether-modified biomass resin foamed material.
S43, polyether-modified biomass resin foamed material, material solidification assembly time prepared using the method for cast in situs
About 5-15min.It can be used for large format dividing plate and compartment casing.
S44, foaming material performance：Density 0.09gcm-1, compressive strength 0.28MPa, thermal conductivity factor 0.050-
0.060W/ (mk), oxygen index (OI) 30%.
Embodiment 5
S51, biomass liquefying resin modified.PPG 330 is added into more biomass liquefying resins, is in temperature
Under the conditions of 30-40 DEG C, stir, regulation pH value is 10, and adding proportion biomass liquefying portions of resin PPG is 5:
1。
S52, biomass are resin expanded.In mass, 100 parts of modified biomass liquefied resins are weighed, 8 parts of surfaces is added and lives
Property agent (Tween-80: OP-10=1: 1), 25 parts of curing agent (phosphoric acid: p-methyl benzenesulfonic acid=3: 1), 5 parts of foaming agents (pentane),
60 parts of isocyanates (PM200).Compound is stirred, in cast in situs, the curing molding under the conditions of normal temperature (25 DEG C), obtained
To polyether-modified biomass resin foamed material.
S53, polyether-modified biomass resin foamed material, material solidification assembly time prepared using the method for cast in situs
About 5-15min.It can be used for large format dividing plate and compartment casing.
S54, foaming material performance：Density 0.07gcm-1, compressive strength 0.30MPa, thermal conductivity factor 0.045-
0.055W/ (mk), oxygen index (OI) 35%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. the preparation method of polyether-modified biomass resin foamed rapidly at normal temperature, it is characterised in that comprise the following steps：
S1, biomass liquefying resin modified：
After PPG and biomass liquefying resin in mass ratio 1: 5-1: 20 are mixed, under the conditions of temperature is 30-40 DEG C,
Stir, regulation pH value is 9-10；
S2, biomass are resin expanded：
By mass, the modified biomass liquefied resin obtained by 100 parts of step S1 is weighed, adds 8-12 part surfactants, 20-
30 parts of curing agent, 5-10 part foaming agents, 50-60 part isocyanates, compound stir, and inject mould or cast in situs,
Curing molding under normal temperature condition, obtain polyether-modified biomass resin foamed material；
The biomass liquefying resin is prepared by following steps：
It is right by the use of hydrochloric acid or sulfuric acid as catalyst using the mixture of phenol or phenol and PEG-4000 as liquefier
The biological material of the mesh of 40 mesh -100 is liquefied, and then in the basic conditions, adds formaldehyde or paraformaldehyde synthesis expandability
Biomass liquefying resin, wherein, phenol and PEG-4000 mass ratio are 100: 0-50: 50.
2. the preparation method of polyether-modified biomass resin foamed rapidly at normal temperature according to claim 1, it is characterised in that
The surfactant is one or more kinds of mixing of Tween-80, OP-10, castor oil nonionic surface active agent
Thing.
3. the preparation method of polyether-modified biomass resin foamed rapidly at normal temperature according to claim 1, it is characterised in that
The curing agent is phosphoric acid, one or several kinds of mixtures of p-methyl benzenesulfonic acid.
4. the preparation method of polyether-modified biomass resin foamed rapidly at normal temperature according to claim 1, it is characterised in that
The foaming agent is pentane, isopentane, one or more of mixtures of petroleum ether.
5. the preparation method of polyether-modified biomass resin foamed rapidly at normal temperature according to claim 1, it is characterised in that
The isocyanates is NPU-MR200, one kind in ten thousand magnificent PM200, BASF M20S, Bayer 44V20L, Hensel advanced in years 5005.
6. the preparation method of polyether-modified biomass resin foamed rapidly at normal temperature according to claim 1, it is characterised in that
The PPG is one or more of mixtures in polyethers 3628, polyethers 330, polyethers 4110, polyethers DL400.
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| CN111285992A (en) * | 2020-03-17 | 2020-06-16 | 浙江工业大学 | Method for preparing foamed cultivation substrate material by adopting bamboo liquefied resin |
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| CN102532800A (en) * | 2011-12-14 | 2012-07-04 | 浙江绿卓科技有限公司 | Biomass phenolic foam and preparation method thereof |
| CN102617883A (en) * | 2012-02-28 | 2012-08-01 | 浙江省林业科学研究院 | Method for preparing foaming material by adopting bamboo liquefied product |
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| CN101885856B (en) * | 2010-07-02 | 2012-07-04 | 北京化工大学 | Method for preparing isocyanate terminated polyether/phenolic resin foamed plastic |
| CN102585141B (en) * | 2011-01-14 | 2013-07-31 | 中国林业科学研究院木材工业研究所 | Flame-retardant polyurethane foam and preparation method thereof |
| CN102585142B (en) * | 2011-01-14 | 2013-09-04 | 中国林业科学研究院木材工业研究所 | Biomass polyurethane foam and method for preparing same |
| CN103601866B (en) * | 2013-11-26 | 2015-11-04 | 北京联合大学生物化学工程学院 | A kind of method utilizing plant polyatomic alcohol synthesis of polyurethane foam materials |
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| CN102532800A (en) * | 2011-12-14 | 2012-07-04 | 浙江绿卓科技有限公司 | Biomass phenolic foam and preparation method thereof |
| CN102617883A (en) * | 2012-02-28 | 2012-08-01 | 浙江省林业科学研究院 | Method for preparing foaming material by adopting bamboo liquefied product |
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