CN107880246A - A kind of methylglucoside PPG insulation material - Google Patents
A kind of methylglucoside PPG insulation material Download PDFInfo
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- CN107880246A CN107880246A CN201711166167.5A CN201711166167A CN107880246A CN 107880246 A CN107880246 A CN 107880246A CN 201711166167 A CN201711166167 A CN 201711166167A CN 107880246 A CN107880246 A CN 107880246A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08B31/00—Preparation of derivatives of starch
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08J9/0066—Use of inorganic compounding ingredients
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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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
- C08J2203/144—Perhalogenated saturated hydrocarbons, e.g. F3C-CF3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- Inorganic Chemistry (AREA)
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- Polyurethanes Or Polyureas (AREA)
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Abstract
The invention discloses a kind of insulation material applied to solar water heater water tank of PPG containing methylglucoside, by DMI and polyether glycol composition with 1~1.5:1 ratio mixed foaming is made.The polyether glycol composition includes methylglucoside PPG, water, chitosan, HFC 356, catalyst, water-soluble silicon oil and aluminium hydroxide.Advantages of nontoxic raw materials of the present invention is harmless, and human body and environment are had no adverse effects.The insulation material of the present invention overcomes the shortcomings that foaming after-contraction is big, avoids water tank deformation, rises and heave stupefied or even cracking phenomenon, and ensure that the heat-insulating property and heat-proof quality of water-heater water tank.
Description
Technical field
The present invention relates to polyurethane heat insulation material technical field, is applied to solar water more particularly to one kind
The polyurethane hard foam insulation material of device water tank.
Background technology
As the energy is increasingly in short supply and the continuous increase of environmental protection pressure, countries in the world all start to push exploitation renewable energy
Source, wherein solar energy are the regenerative resource utilized and exploitation is most wide, development prospect is best, and it is each to be widely used in each row
Industry, solar water heater industry are exactly one of them.China is richly stored with solar energy resources, and Solar use prospect is wide
It is wealthy, it has been that the first of solar water heater in the world uses state and producing country at present.
The insulation material that can serve as water tank at present mainly has polyurethane foam, phenol formaldehyde foam, superfine fibre etc..Polyurethane foam
Foam is to be mixed to be poured into foam in mould or water tank cavity with polyether composition by isocyanates to be made, and wherein polyether composition contains
There are PPG, foaming agent, catalyst, stabilizer etc., moulding process is simple, thermal conductivity factor is low because polyurethane foam has
It is the insulation material that water tank mainly uses etc. advantage.
Polyurethane hard foam in process of production, because of itself characteristic, production technology and direct labor's operative skill etc.
The reason for each side, the problem of generally existing foam contraction, foam is easily caused to come off with casing part or all come off, finally
Cause casing deformation, vacuum mouth of pipe foam cracking, the polyurethane hard foam that What is more between inner bag and shell is laterally or longitudinally
Cracking, greatly reduce the heat insulation effect of water tank.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of thermal insulating material of PPG containing methylglucoside
Material, the material overcome the shortcomings that foaming after-contraction is big, avoid water tank deformation, rise and heave stupefied or even cracking phenomenon,
And it ensure that the heat-insulating property and heat-proof quality of water-heater water tank.
Technical scheme is as follows：
A kind of insulation material of the PPG containing methylglucoside, material by DMI and polyether glycol composition with 1~
1.5:1 ratio mixed foaming is made.The polyether glycol composition includes the raw material of following parts by weight：Methylglucoside
It is 70~90 parts of PPG, 10~20 parts of water, 4~8 parts of chitosan, 0.5~2 part of HFC-356,1~4 part of catalyst, water-soluble
Property 0.5~2 part of silicone oil and 10~20 parts of aluminium hydroxide.
Described catalyst is dimethylethanolamine and dibutyl tin laurate using weight ratio as 1.5~2:1 mixing
Mixture.
The methylglucoside PPG be by ratio be 1:2 farinas (aqueous 10~15%) and methanol
Put into autoclave, then add appropriate C2H3BF3O, temperature is raised to 130~140 DEG C with 20~30 minutes after nitrogen displacement,
And maintain 30 minutes.Room temperature (in 5~10 minutes) is cooled to, crude product is filtered, steams part methanol, finally separate methyl Portugal
Grape glucoside crystallizes, then is obtained after being dried by drying equipment.Filtrate (mainly methanol and starch degradation liquid) can be sent in acidity
Return in autoclave and re-use, so that the starch and the methanol that make to have degraded further react generation methylglucoside.Work as filtrate
Apply mechanically more than four times, the yield of methyl a-D- glucose can be more than 95%.In addition, product methyl glucose is separated from reaction product
It glucoside, can not have to filtering yet, the first of moisture and unreacted is directly boiled off under 60~80 DEG C/25~50 millimeters of vacuum condition
Alcohol, residue are methylglucoside.Catalyst can also use sulphonic acids.
The chitosan is molecular weight l0 ten thousand to 1,000,000, uses the preceding acetic acid with l%~3%.Add low molecule amount
Chitosan, enable to the polyethers material after foaming that there is interconnected hole, also there is aperture, chitosan between big hole wall
Absorption is not easy to vanish in internal surface of hole, caused abscess, can also make aperture increases, so that the expansion rate of polyethers material carries
Height, heat insulation effect significantly improve.
The preparation method of the insulation material comprises the following steps：
（1）Take 70~90 parts of methylglucoside PPG, 10~20 parts of water, 4~8 parts of chitosan, HFC-356 0.5~
10~20 parts of 2 parts, 1~4 part of catalyst, 0.5~2 part of water-soluble silicon oil and aluminium hydroxide, it is well mixed to obtain PPG
Composition；
（2）By DMI and polyether glycol composition in mass ratio 1~1.5:1 mixing is poured into solar water heater water tank cavity
Inside foamed, produced after hot setting.
The beneficial effects of the invention are as follows：
Advantages of nontoxic raw materials of the present invention is harmless, and human body and environment are had no adverse effects.The methylglucoside of the present invention gathers
Ethoxylated polyhydric alcohol is synthesized by starch processing, and raw material sources are extensive, and cost is cheap, and process is safe and reliable.The present invention adds low point
The chitosan of son amount, enable to the polyethers material after foaming that there is interconnected hole, also there is aperture, shell between big hole wall
Glycan absorption is not easy to vanish in internal surface of hole, caused abscess, can also make aperture increases, so that the expansion of polyethers material
Rate improves, and heat insulation effect significantly improves.The foaming agent of the present invention uses HFC-356, nontoxic, non-ignitable, safe to use, and thermal conductivity
Low, ODP values are zero, and GWP value is close to zero.Polyurethane rigid foam plastic is prepared using HFC-356, is advantageous to improve insulation material
Heat-insulating property and heat-proof quality.Aluminium hydroxide has that nontoxic, stability is good as a kind of inorganic combustion inhibitor, is not produced under high temperature
Raw toxic gas, moreover it is possible to the advantages that smoke amount when reducing material combustion, and cheap, wide material sources.
Embodiment
The present invention is introduced in order to more detailed, with reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of insulation material of PPG containing methylglucoside, material is by DMI and polyether glycol composition with 1.2:1
Ratio mixed foaming is made.The polyether glycol composition includes the raw material of following parts by weight：Methylglucoside polyethers
80 parts of polyalcohol, 15 parts of water, 6 parts of chitosan, 1 part of HFC-356,2 parts of catalyst, 1 part of water-soluble silicon oil and aluminium hydroxide 15
Part.
The methylglucoside PPG be by ratio be 1:2 farinas (aqueous 13%) and methanol input
In autoclave, then add appropriate C2H3BF3O, temperature is raised to 135 DEG C with 25 minutes after nitrogen displacement, and maintained 30 minutes.
Room temperature (in 5~10 minutes) is cooled to, crude product is filtered, steams part methanol, finally separates the crystallization of methyl glucose essence glucoside, then lead to
Cross after drying equipment is dried and obtain.
The chitosan is molecular weight l0 ten thousand to 1,000,000, using it is preceding with 2% acetic acid.Described catalyst is two
Methylethanolamine and dibutyl tin laurate are using weight ratio as 1.8:The mixture of 1 mixing.
The preparation method of the insulation material comprises the following steps：
（1）Take 80 parts of methylglucoside PPG, 15 parts of water, 6 parts of chitosan, 1 part of HFC-356,2 parts of catalyst, water
15 parts of 1 part of dissolubility silicone oil and aluminium hydroxide, it is well mixed to obtain polyether glycol composition；
（2）By DMI and polyether glycol composition in mass ratio 1.2:1 mixing is poured into solar water heater water tank cavity
Row foaming, is produced after hot setting.
Embodiment 2
A kind of insulation material of PPG containing methylglucoside, material is by DMI and polyether glycol composition with 1:1 ratio
Example mixed foaming is made.The polyether glycol composition includes the raw material of following parts by weight：Methylglucoside polyethers is more
First 70 parts of alcohol, 10 parts of water, 4 parts of chitosan, 0.5 part of HFC-356,1 part of catalyst, 0.5 part of water-soluble silicon oil and aluminium hydroxide 10
Part.
The methylglucoside PPG be by ratio be 1:2 farinas (aqueous 10%) and methanol input
In autoclave, then add appropriate C2H3BF3O, temperature is raised to 130 DEG C with 20 minutes after nitrogen displacement, and maintained 30 minutes.
Room temperature (in 5~10 minutes) is cooled to, crude product is filtered, steams part methanol, finally separates methylglucoside crystallization, then lead to
Cross after drying equipment is dried and obtain.
The chitosan is molecular weight l0 ten thousand to 1,000,000, uses the preceding acetic acid with l%.Described catalyst is two
Methylethanolamine and dibutyl tin laurate are using weight ratio as 1.5:The mixture of 1 mixing.
The preparation method of the insulation material comprises the following steps：
（1）Take 70 parts of methylglucoside PPG, 10 parts of water, 4 parts of chitosan, 0.5 part of HFC-356,1 part of catalyst,
10 parts of 0.5 part of water-soluble silicon oil and aluminium hydroxide, it is well mixed to obtain polyether glycol composition；
（2）By DMI and polyether glycol composition in mass ratio 1:1 mixing, which is poured into solar water heater water tank cavity, to be carried out
Foaming, is produced after hot setting.
Embodiment 3
A kind of insulation material of PPG containing methylglucoside, material is by DMI and polyether glycol composition with 1.5:
1 ratio mixed foaming is made.The polyether glycol composition includes the raw material of following parts by weight：Methylglucoside polyethers
20 parts of 90 parts of polyalcohol, water, 8 parts of chitosan, 2 parts of HFC-356,4 parts of catalyst, 2 parts of water-soluble silicon oil and aluminium hydroxide.
The methylglucoside PPG be by ratio be 1:2 farinas (aqueous 13%) and methanol input
In autoclave, then add appropriate C2H3BF3O, temperature is raised to 140 DEG C with 30 minutes after nitrogen displacement, and maintained 30 minutes.
Room temperature (in 5~10 minutes) is cooled to, crude product is filtered, steams part methanol, finally separates methylglucoside crystallization, then lead to
Cross after drying equipment is dried and obtain.
The chitosan is molecular weight l0 ten thousand to 1,000,000, using it is preceding with 3% acetic acid.Described catalyst is two
Methylethanolamine and dibutyl tin laurate are using weight ratio as 2:The mixture of 1 mixing.
The preparation method of the insulation material comprises the following steps：
（1）Take 90 parts of methylglucoside PPG, 20 parts of water, 8 parts of chitosan, 2 parts of HFC-356,4 parts of catalyst, water
20 parts of 2 parts of dissolubility silicone oil and aluminium hydroxide, it is well mixed to obtain polyether glycol composition；
（2）By DMI and polyether glycol composition in mass ratio 1.5:1 mixing is poured into solar water heater water tank cavity
Row foaming, is produced after hot setting.
Application Example
More fully to illustrate the present invention, the applicant has manufactured two solar water heaters and has carried out performance tests, wherein one too
Positive energy water-heater water tank is using the polyurethane foam material of company of the Guangdong Province production of in the market purchase as insulation material（It is right
According to group）, the insulation material of another PPG containing methylglucoside using the present invention（Experimental group）.In cloudy weather
（18~25 DEG C of temperature）Under the conditions of, the highest water temperature of control group is up to 80 DEG C, and for the highest water temperature of experimental group up to 86 DEG C, this illustrates this hair
Bright insulation material heat insulation effect is better.
The moulded foam of control group and experimental group is taken respectively and detects its performance parameter, performance indications such as following table：
From table, the index such as the compressive strength of insulation material heat-insulation layer of the present invention, molding shrinkage is all than existing thermal insulating material
Material, which has, significantly to be improved, and is a kind of excellent performance under chilled or hot conditions phenomena such as ungauged regions, deformation, expansion, cracking
Insulation material.
Application Example of the insulation material of the PPG containing methylglucoside of the present invention in fire prevention：
By the insulation material and thickness, equirotal existing poly- ammonia therewith of the PPG containing methylglucoside of the present invention
Ester stiff foam material（Black material+white material）Calcination 10 minutes under the flame of natural liquid gases cooking stove are placed in simultaneously, are as a result found, it is existing
There is polyurethane hard foam material catching fire, insulation material of the invention does not burn.
Claims (5)
1. the insulation material of a kind of PPG containing methylglucoside, it is characterised in that the insulation material is by DMI and gathers
Ethoxylated polyhydric alcohol composition is with 1~1.5:1 ratio mixed foaming is made.
2. the insulation material of the PPG containing methylglucoside according to claim 1, it is characterised in that the polyethers
Glycol composition includes the raw material of following parts by weight：
70~90 parts of methylglucoside PPG；
10~20 parts of water；
4~8 parts of chitosan；
0.5~2 part of HFC-356；
1~4 part of catalyst；
0.5~2 part of water-soluble silicon oil；
10~20 parts of aluminium hydroxide；
Described catalyst is dimethylethanolamine and dibutyl tin laurate using weight ratio as 1.5~2:The mixing of 1 mixing
Thing.
3. the insulation material of the PPG containing methylglucoside according to claim 1, it is characterised in that the methyl
Glycoside PPG be by ratio be 1:In 2 farinas and methanol input autoclave, then add appropriate
C2H3BF3O, temperature is raised to 130~140 DEG C with 20~30 minutes after nitrogen displacement, and maintained 30 minutes；It is cooled to room temperature,
Crude product is filtered, steams part methanol, finally separates methylglucoside crystallization, then obtained after being dried by drying equipment.
4. the insulation material of the PPG containing methylglucoside according to claim 1, it is characterised in that the shell gathers
Sugar is molecular weight l0 ten thousand to 1,000,000, uses the preceding acetic acid with l%~3%.
5. the insulation material of the PPG containing methylglucoside according to claim 1, it is characterised in that the insulation
The preparation method of material comprises the following steps：
（1）Take 70~90 parts of methylglucoside PPG, 10~20 parts of water, 4~8 parts of chitosan, HFC-356 0.5~
10~20 parts of 2 parts, 1~4 part of catalyst, 0.5~2 part of water-soluble silicon oil and aluminium hydroxide, it is well mixed to obtain PPG
Composition；
（2）By DMI and polyether glycol composition in mass ratio 1~1.5:1 mixing is poured into solar water heater water tank cavity
Inside foamed, produced after hot setting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711166167.5A CN107880246A (en) | 2017-11-21 | 2017-11-21 | A kind of methylglucoside PPG insulation material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711166167.5A CN107880246A (en) | 2017-11-21 | 2017-11-21 | A kind of methylglucoside PPG insulation material |
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| CN107880246A true CN107880246A (en) | 2018-04-06 |
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| CN201711166167.5A Pending CN107880246A (en) | 2017-11-21 | 2017-11-21 | A kind of methylglucoside PPG insulation material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333308A (en) * | 2013-07-15 | 2013-10-02 | 广西超星太阳能科技有限公司 | Perlite foaming thermal insulation material of water tank of solar water heater |
| CN103435769A (en) * | 2013-07-15 | 2013-12-11 | 广西超星太阳能科技有限公司 | Inorganic fireproof foamed thermal-insulation material for water tank of solar water heater |
| CN106279630A (en) * | 2016-08-25 | 2017-01-04 | 胡国旺 | Floride-free type polyurethane insulation material |
-
2017
- 2017-11-21 CN CN201711166167.5A patent/CN107880246A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333308A (en) * | 2013-07-15 | 2013-10-02 | 广西超星太阳能科技有限公司 | Perlite foaming thermal insulation material of water tank of solar water heater |
| CN103435769A (en) * | 2013-07-15 | 2013-12-11 | 广西超星太阳能科技有限公司 | Inorganic fireproof foamed thermal-insulation material for water tank of solar water heater |
| CN106279630A (en) * | 2016-08-25 | 2017-01-04 | 胡国旺 | Floride-free type polyurethane insulation material |
Non-Patent Citations (2)
| Title |
|---|
| 刘兴允: "淀粉聚醚多元醇", 《聚氨酯工业》 * |
| 李明: "甲甙聚醚多元醇的合成及其应用", 《沈阳化工》 * |
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