CN106280231A - A kind of sports equipment toughening modifying phenolic foam and preparation method thereof - Google Patents
A kind of sports equipment toughening modifying phenolic foam and preparation method thereof Download PDFInfo
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- CN106280231A CN106280231A CN201610661850.5A CN201610661850A CN106280231A CN 106280231 A CN106280231 A CN 106280231A CN 201610661850 A CN201610661850 A CN 201610661850A CN 106280231 A CN106280231 A CN 106280231A
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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
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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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- 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
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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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/14—Modified phenol-aldehyde condensates
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
A kind of sports equipment toughening modifying phenolic foam, relating to phenolic foam field, it is prepared from by the raw material of following portions by weight: 35 45 parts of phenolic resin, phenol-formaldehyde resin modified 26 32 parts, fine silica powder 0.5 2 parts, modified former bamboo fibre 13 parts, foaming agent 36 parts, 58 parts of surfactant, 16 20 parts of firming agent, antioxidant 15 parts；Described surfactant is made up of polyoxyethylene fatty acid ester, dodecylbenzene sodium sulfonate and ethanol；Described phenol-formaldehyde resin modified is prepared by the aggregated reaction of the raw material of following portions by weight: phenol 100 parts, 80 90 parts of formaldehyde, oleic acid 35 parts, oxalic acid 7 10 parts, mass concentration are the hydrochloric acid 1.5 3.5 parts of 31%.The sports equipment phenolic foam product that the present invention prepares has good toughness, improves phenolic foam fragility and greatly, easily falls the problem of slag, ensure that product has excellent mechanical property and fire resistance simultaneously.
Description
Technical field
The present invention relates to phenolic foam field, be specifically related to a kind of sports equipment toughening modifying phenolic foam
And preparation method thereof.
Background technology
Phenolic foam density is low, lightweight, and heat conductivity is low, uses temperature model same big, good stability of the dimension.Compare
In polyvinyl chloride foam, polyethylene, polyurethane foam, phenol formaldehyde foam has the difficult combustion of excellence, self-extinguishment, low smog, fire-resistant
The advantage that flame runs through.Therefore, phenolic foam obtains in fields such as building, boats and ships, air material, sports equipments in recent years
It is widely applied.
But, closely the piling up of rigidity aromatic ring connected due to phenolic foam molecular structure methylene, phenolic hydroxyl group
Easily aoxidize with methylene so that the oxidative resistance of phenolic foam self is bad, and mechanical property is poor, especially fragility
Greatly, easy efflorescence, this defect significantly limit its application.And current, along with the diversified development of sports item, and
The raising of people's health sense, the kind of sports equipment is also being on the increase, and people are to the safety of sports equipment, comfortable simultaneously
Property etc. require more and more higher.From the point of view of excellent sports equipment phenolic foam product, typically require that it has excellent
The performances such as good wear-resisting, buffering, shockproof, fire-retardant, light weight, based on this, the present invention provides a kind of sports equipment toughening modifying phenol
Formaldehyde foam plastic, to meet its use requirement.
Summary of the invention
It is an object of the invention to provide a kind of sports equipment toughening modifying phenolic foam and preparation method thereof, make system
The sports equipment phenolic foam product obtained has good toughness, improves its fragility and greatly, easily falls the problem of slag, protects simultaneously
Card product has excellent mechanical property and fire resistance.
For achieving the above object, the technical solution adopted in the present invention is: a kind of sports equipment toughening modifying phenolic aldehyde bubble
Foam plastics, it is prepared from by the raw material of following portions by weight: phenolic resin 35-45 part, phenol-formaldehyde resin modified 26-32 part, two
Ultrafine silica powder 0.5-2 part, modified former bamboo fibre 1-3 part, foaming agent 3-6 part, surfactant 5-8 part, firming agent 16-20
Part, antioxidant 1-5 part；Described surfactant is made up of polyoxyethylene fatty acid ester, dodecylbenzene sodium sulfonate and ethanol；
Described phenol-formaldehyde resin modified is prepared by the aggregated reaction of the raw material of following portions by weight: phenol 100 parts, formaldehyde 80-90 part, oil
Acid 3-5 part, oxalic acid 7-10 part, mass concentration are hydrochloric acid 1.5-3.5 part of 31%.
Further, the preparation method of the former bamboo fibre of described modification is: former bamboo fibre is first placed in acetic acid, hydrochloric acid and water group
The mixed liquor become soaks 1-2h, then, after the washing of former bamboo fibre, drying, is placed in linolenic diethyl ether solution, and
Be heated to reflux 1-3h at 50-60 DEG C, the most scrubbed, dry after, obtain the former bamboo fibre of described modification；Wherein, described acetic acid, salt
In the mixed liquor of acid and water composition, the mass fraction of hydrochloric acid is 8-10%, and the mass fraction of acetic acid is 3-6%.
The preparation method of described phenol-formaldehyde resin modified is: by proportioning, described raw material is added reaction vessel, and heating in water bath is also
At the uniform velocity stirring, bath temperature is 80 DEG C, and mixing speed is 200 turns/min, pre-reaction 2.5h；Then the pH value of reactant liquor is regulated
To 2, back flow reaction 1.5h at 90 DEG C；After polyreaction terminates, carry out decompression dehydration, i.e. prepare phenol-formaldehyde resin modified.
The particle diameter of described fine silica powder is 300nm-600nm, and its surface is through silane coupler modified process.
Described foaming agent is any one or more in pentane, isopentane, normal hexane and Pentamethylene..
Described firming agent is made up of the sulphuric acid that mass ratio is 1:1-2 and p-methyl benzenesulfonic acid, and the mass concentration of sulphuric acid is 40%-
50%。
Described antioxidant is phosphite ester kind antioxidant.
A kind of preparation method of the sports equipment toughening modifying phenolic foam of the present invention, its step is as follows:
(1), by described weight proportion, each raw material is taken, standby；
(2), taking in phenolic resin and phenol-formaldehyde resin modified addition reaction vessel, heating in water bath also at the uniform velocity stirs, and bath temperature is
80 DEG C, mixing speed is 300 turns/min, stirs 1h；
(3), adding fine silica powder and the former bamboo fibre of modification in reaction vessel, 500 turns/min at the uniform velocity stirs 1h；
(4), in reaction vessel, add foaming agent, surfactant and antioxidant, keep 500 turns/min at the uniform velocity to stir
5min, is allowed to mix homogeneously；
(5), in reaction vessel, add firming agent, under 900 turns/min, stir 1min；
(6), by the mixture mold filling in reaction vessel, solidify at 75 DEG C, foam, the demoulding after 1h,.
Beneficial effect:
The present invention is by adding phenol-formaldehyde resin modified, fine silica powder, and modified former bamboo fibre in phenolic resin base material
Composition, and prepare final sports equipment toughening modifying phenolic foam product by foam process, products obtained therefrom has
Excellent toughness, and ensure that mechanical property and the fire resistance of product.
By adding phenol-formaldehyde resin modified and the modification former bamboo fibre composition of the present invention, improve simple phenol formaldehyde foam and mould
The problem of slag is fallen in material fragility efflorescence big, easy, to improve the toughness of product.Former bamboo fibre first mixing through acetic acid, hydrochloric acid and water composition
Close acid and carry out pretreatment, then carry out chemical modification with linolenic acid, enable the former bamboo fibre of modification and the phenolic foam of gained
Occur good interface cohesion, the most modified former bamboo fibre self to become the most pliable and the toughest, be more beneficial for improving phenolic foam
Toughness.
The present invention, while improving phenolic foam toughness, improves the strong of product by adding fine silica powder
Degree, it is ensured that the mechanical property of product.By choosing suitable fine silica powder particle diameter, and utilize silane coupler to it
Modifying surface processes so that it is disperse to be more uniformly distributed in phenolic foam, higher with the adhesion of phenolic foam.
Detailed description of the invention
Embodiment 1
A kind of sports equipment toughening modifying phenolic foam, it is prepared from by the raw material of following portions by weight: phenolic aldehyde tree
40 parts of fat, phenol-formaldehyde resin modified 30 parts, fine silica powder 1 part, modified former bamboo fibre 2 parts, pentane 5 parts, surfactant 6
Part, 18 parts of firming agent, phosphite ester kind antioxidant 3 parts；Described surfactant is by polyoxyethylene fatty acid ester, detergent alkylate
Sodium sulfonate and ethanol composition；Described phenol-formaldehyde resin modified is prepared by the aggregated reaction of the raw material of following portions by weight: phenol 100
Part, 85 parts of formaldehyde, oleic acid 5 parts, oxalic acid 8 parts, mass concentration are the hydrochloric acid 2 parts of 31%.
The preparation method of described phenol-formaldehyde resin modified is: by proportioning, described raw material is added reaction vessel, and heating in water bath is also
At the uniform velocity stirring, bath temperature is 80 DEG C, and mixing speed is 200 turns/min, pre-reaction 2.5h；Then the pH value of reactant liquor is regulated
To 2, back flow reaction 1.5h at 90 DEG C；After polyreaction terminates, carry out decompression dehydration, i.e. prepare phenol-formaldehyde resin modified.
The preparation method of the former bamboo fibre of described modification is: former bamboo fibre is first placed in acetic acid, hydrochloric acid and the mixing of water composition
Liquid soaks 1-2h, then, after the washing of former bamboo fibre, drying, is placed in linolenic diethyl ether solution, and at 50-60 DEG C
Be heated to reflux 1-3h, the most scrubbed, dry after, obtain the former bamboo fibre of described modification；Wherein, described acetic acid, hydrochloric acid and water group
In the mixed liquor become, the mass fraction of hydrochloric acid is 8-10%, and the mass fraction of acetic acid is 3-6%.
The particle diameter of described fine silica powder is 300nm-600nm, and its surface is through silane coupler modified process.
Described firming agent is made up of the sulphuric acid that mass ratio is 1:1-2 and p-methyl benzenesulfonic acid, and the mass concentration of sulphuric acid is 40%-
50%。
A kind of preparation method of the sports equipment toughening modifying phenolic foam of the present embodiment, its step is as follows:
(1), by described weight proportion, each raw material is taken, standby；
(2), taking in phenolic resin and phenol-formaldehyde resin modified addition reaction vessel, heating in water bath also at the uniform velocity stirs, and bath temperature is
80 DEG C, mixing speed is 300 turns/min, stirs 1h；
(3), adding fine silica powder and the former bamboo fibre of modification in reaction vessel, 500 turns/min at the uniform velocity stirs 1h；
(4), in reaction vessel, add foaming agent (i.e. pentane), surfactant and phosphite ester kind antioxidant, keep 500
Turn/min at the uniform velocity stirs 5min, is allowed to mix homogeneously；
(5), in reaction vessel, add firming agent, under 900 turns/min, stir 1min；
(6), by the mixture mold filling in reaction vessel, solidify at 75 DEG C, foam, the demoulding after 1h,.
Embodiment 2
A kind of sports equipment toughening modifying phenolic foam, it is prepared from by the raw material of following portions by weight: phenolic aldehyde tree
35 parts of fat, phenol-formaldehyde resin modified 32 parts, fine silica powder 1 part, modified former bamboo fibre 1 part, isopentane 3 parts, surfactant 5
Part, 18 parts of firming agent, phosphite ester kind antioxidant 2 parts；Described surfactant is by polyoxyethylene fatty acid ester, detergent alkylate
Sodium sulfonate and ethanol composition；Described phenol-formaldehyde resin modified is prepared by the aggregated reaction of the raw material of following portions by weight: phenol 100
Part, 80 parts of formaldehyde, oleic acid 3 parts, oxalic acid 8 parts, mass concentration are the hydrochloric acid 1.5 parts of 31%.
In the present embodiment, phenol-formaldehyde resin modified, modified former bamboo fibre, and the preparation method of phenolic foam product is equal
Same as in Example 1.Fine silica powder used and firming agent are the most same as in Example 1.
Embodiment 3
A kind of sports equipment toughening modifying phenolic foam, it is prepared from by the raw material of following portions by weight: phenolic aldehyde tree
45 parts of fat, phenol-formaldehyde resin modified 32 parts, fine silica powder 2 parts, modified former bamboo fibre 3 parts, normal hexane 6 parts, surfactant 8
Part, 20 parts of firming agent, phosphite ester kind antioxidant 5 parts；Described surfactant is by polyoxyethylene fatty acid ester, detergent alkylate
Sodium sulfonate and ethanol composition；Described phenol-formaldehyde resin modified is prepared by the aggregated reaction of the raw material of following portions by weight: phenol 100
Part, 90 parts of formaldehyde, oleic acid 5 parts, oxalic acid 10 parts, mass concentration are the hydrochloric acid 3 parts of 31%.
In the present embodiment, phenol-formaldehyde resin modified, modified former bamboo fibre, and the preparation method of phenolic foam product is equal
Same as in Example 1.Fine silica powder used and firming agent are the most same as in Example 1.
Embodiment 4
A kind of sports equipment toughening modifying phenolic foam, it is prepared from by the raw material of following portions by weight: phenolic aldehyde tree
35 parts of fat, phenol-formaldehyde resin modified 26 parts, fine silica powder 2 parts, modified former bamboo fibre 2 parts, Pentamethylene. 3 parts, surfactant 6
Part, 16 parts of firming agent, phosphite ester kind antioxidant 3 parts；Described surfactant is by polyoxyethylene fatty acid ester, detergent alkylate
Sodium sulfonate and ethanol composition；Described phenol-formaldehyde resin modified is prepared by the aggregated reaction of the raw material of following portions by weight: phenol 100
Part, 90 parts of formaldehyde, oleic acid 3 parts, oxalic acid 10 parts, mass concentration are the hydrochloric acid 1.5 parts of 31%.
In the present embodiment, phenol-formaldehyde resin modified, modified former bamboo fibre, and the preparation method of phenolic foam product is equal
Same as in Example 1.Fine silica powder used and firming agent are the most same as in Example 1.
Embodiment 5
A kind of sports equipment toughening modifying phenolic foam, it is prepared from by the raw material of following portions by weight: phenolic aldehyde tree
40 parts of fat, phenol-formaldehyde resin modified 26 parts, fine silica powder 1.5 parts, modified former bamboo fibre 2 parts, Pentamethylene. 5 parts, surface activity
Agent 6 parts, 18 parts of firming agent, phosphite ester kind antioxidant 2 parts；Described surfactant is by polyoxyethylene fatty acid ester, dodecane
Base benzene sulfonic acid sodium salt and ethanol composition；Described phenol-formaldehyde resin modified is prepared by the aggregated reaction of the raw material of following portions by weight: benzene
100 parts of phenol, 80 parts of formaldehyde, oleic acid 5 parts, oxalic acid 7 parts, mass concentration are the hydrochloric acid 3.5 parts of 31%.
In the present embodiment, phenol-formaldehyde resin modified, modified former bamboo fibre, and the preparation method of phenolic foam product is equal
Same as in Example 1.Fine silica powder used and firming agent are the most same as in Example 1.
The performance test of the modified phenolic foam plastic prepared by the various embodiments described above is as follows:
The performance test results of the modified phenolic foam plastic prepared by table 1 various embodiments of the present invention
As can be seen from Table 1: the modified phenolic foam plastic product prepared by various embodiments of the present invention is respectively provided with higher compression
Intensity and bending strength, the toughness of product and mechanical property all show excellent, and pulverization rate is low, and have high flame resistance, product
Combination property is preferable, it is possible to meet the high standard requirement of sports equipment product.
Claims (8)
1. a sports equipment toughening modifying phenolic foam, it is characterised in that: it is by the raw material system of following portions by weight
For forming: phenolic resin 35-45 part, phenol-formaldehyde resin modified 26-32 part, fine silica powder 0.5-2 part, modified former bamboo fibre 1-
3 parts, foaming agent 3-6 part, surfactant 5-8 part, firming agent 16-20 part, antioxidant 1-5 part；Described surfactant by
Polyoxyethylene fatty acid ester, dodecylbenzene sodium sulfonate and ethanol composition；Described phenol-formaldehyde resin modified is by following portions by weight
The aggregated reaction of raw material and prepare: phenol 100 parts, formaldehyde 80-90 part, oleic acid 3-5 part, oxalic acid 7-10 part, mass concentration are 31%
Hydrochloric acid 1.5-3.5 part.
2. a kind of sports equipment toughening modifying phenolic foam as claimed in claim 1, it is characterised in that: described modification
The preparation method of former bamboo fibre is: is first placed in by former bamboo fibre in the mixed liquor of acetic acid, hydrochloric acid and water composition and soaks 1-2h, so
After, after the washing of former bamboo fibre, drying, it is placed in linolenic diethyl ether solution, and is heated to reflux 1-3h at 50-60 DEG C,
After washing, drying, obtain the former bamboo fibre of described modification；Wherein, in the mixed liquor of described acetic acid, hydrochloric acid and water composition, salt
The mass fraction of acid is 8-10%, and the mass fraction of acetic acid is 3-6%.
3. a kind of sports equipment toughening modifying phenolic foam as claimed in claim 1, it is characterised in that: described modification
The preparation method of phenolic resin is: by proportioning, described raw material is added reaction vessel, and heating in water bath also at the uniform velocity stirs, bath temperature
Being 80 DEG C, mixing speed is 200 turns/min, pre-reaction 2.5h；Then regulating the pH value of reactant liquor to 2, at 90 DEG C, backflow is anti-
Answer 1.5h；After polyreaction terminates, carry out decompression dehydration, i.e. prepare phenol-formaldehyde resin modified.
4. a kind of sports equipment toughening modifying phenolic foam as claimed in claim 1, it is characterised in that: described dioxy
The particle diameter of SiClx micropowder is 300nm-600nm, and its surface is through silane coupler modified process.
5. a kind of sports equipment toughening modifying phenolic foam as claimed in claim 1, it is characterised in that: described foaming
Agent is any one or more in pentane, isopentane, normal hexane and Pentamethylene..
6. a kind of sports equipment toughening modifying phenolic foam as claimed in claim 1, it is characterised in that: described solidification
Agent is made up of the sulphuric acid that mass ratio is 1:1-2 and p-methyl benzenesulfonic acid, and the mass concentration of sulphuric acid is 40%-50%.
7. a kind of sports equipment toughening modifying phenolic foam as claimed in claim 1, it is characterised in that: described antioxygen
Agent is phosphite ester kind antioxidant.
8. the preparation method of a kind of sports equipment toughening modifying phenolic foam as described in any one of claim 1-7,
It is characterized in that: step is as follows:
(1), by described weight proportion, each raw material is taken, standby；
(2), taking in phenolic resin and phenol-formaldehyde resin modified addition reaction vessel, heating in water bath also at the uniform velocity stirs, and bath temperature is
80 DEG C, mixing speed is 300 turns/min, stirs 1h；
(3), adding fine silica powder and the former bamboo fibre of modification in reaction vessel, 500 turns/min at the uniform velocity stirs 1h；
(4), in reaction vessel, add foaming agent, surfactant and antioxidant, keep 500 turns/min at the uniform velocity to stir
5min, is allowed to mix homogeneously；
(5), in reaction vessel, add firming agent, under 900 turns/min, stir 1min；
(6), by the mixture mold filling in reaction vessel, solidify at 75 DEG C, foam, the demoulding after 1h,.
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| CN106905656A (en) * | 2017-04-10 | 2017-06-30 | 河南科技大学 | A kind of wab board modified phenolic foam composite and preparation method thereof |
| CN107189342A (en) * | 2017-07-12 | 2017-09-22 | 合肥轻风飏电气科技有限责任公司 | A kind of wear-resisting antistatic Yoga mat and preparation method thereof |
| CN107266853A (en) * | 2017-07-18 | 2017-10-20 | 合肥广能新材料科技有限公司 | Phenolic foam heat insulation plate and preparation method thereof |
| CN107312292A (en) * | 2017-07-18 | 2017-11-03 | 合肥广能新材料科技有限公司 | Toughening modifying phenolic foam heat insulation plate and preparation method thereof |
| CN107236246A (en) * | 2017-08-01 | 2017-10-10 | 合肥康之恒机械科技有限公司 | A kind of wab board nano antibacterial composite and preparation method thereof |
| CN107266855A (en) * | 2017-08-14 | 2017-10-20 | 芜湖乾凯材料科技有限公司 | Based on nano-silicon dioxide modified environment-friendlyflame-retardant flame-retardant material and preparation method thereof |
| CN107383767A (en) * | 2017-09-14 | 2017-11-24 | 江苏攸途健身器材有限公司 | A kind of preparation method of wab board modified phenolic foam composite |
| CN107573640A (en) * | 2017-09-14 | 2018-01-12 | 江苏攸途健身器材有限公司 | A kind of wab board modified phenolic foam composite |
| CN108485176A (en) * | 2018-03-15 | 2018-09-04 | 龚利芬 | Fibre-reinforced environmentally friendly phenolic aldehyde thermal insulation material of raw bamboo and preparation method thereof |
| CN108424610A (en) * | 2018-04-23 | 2018-08-21 | 石磊 | A kind of preparation method of flexible Anti-pressure phenolic foam |
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