CN107501594A - A kind of method with gel state nylon blown foams - Google Patents
A kind of method with gel state nylon blown foams Download PDFInfo
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- CN107501594A CN107501594A CN201710727606.9A CN201710727606A CN107501594A CN 107501594 A CN107501594 A CN 107501594A CN 201710727606 A CN201710727606 A CN 201710727606A CN 107501594 A CN107501594 A CN 107501594A
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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
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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
-
- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J2203/08—Supercritical fluid
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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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
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- 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
- C08K3/16—Halogen-containing compounds
Abstract
The present invention relates to foamed plastic field, and in particular to a kind of method with gel state nylon blown foams.By metal salt, polyisobutene by nylon performed polymer gel state, then foam, further make its polymerization-stable using catalyst is steam-cured, form foamed plastics.It the method overcome the defects of nylon directly heats foamed melt slightly low foam wall is easily caved in.Obtained foam not only uniform foam cell, and light intensity is high, technical support is provided to develop the application of nylon foam.
Description
Technical field
The present invention relates to foamed plastic field, and in particular to a kind of method with gel state nylon blown foams.
Background technology
PA plastics are that a company of the U.S. develops resin for fiber at first, realize and industrialize in nineteen thirty-nine.20th century
Start the fifties to develop and produce injection-molded item, the lightweight of downstream industry product is met with substituted metal, reduces the requirement of cost.
PA has good combination property, including mechanical property, heat resistance, wear resistance, chemical proofing and self lubricity, and rubs
It is low to wipe coefficient, there is certain anti-flammability, it is easy to process, suitable for glass fibre and other filler filling enhancing modifieds, raising property
Application and can be expanded.
Contain amide group on nylon molecules main chain, it is polar group, intermolecular in the presence of strong hydrogen bond action, molecule
Chain arranged regular, so nylon crystallinity is high, mechanical performance and excellent shock resistance, metal salt can occur with amide group
Complex reaction, the hydrogen bond between saboteur, it can effectively control the crystallinity of nylon.Nylon is polar polymer, Zhi Nengrong
In some highly polar solvents of Xie Yu, but the mixed solution of the solvent of some low poles and inorganic salts can also dissolve nylon, lead to
Polymer intelligent gelinite can be prepared by crossing this solvent, available for weave, the research of nylon aggregation state change and phase-change material.
PA (nylon, polyamide) plastics have a good combination property, including mechanical property, heat resistance, wear resistance, resistance to
Chemicals and self lubricity, and coefficient of friction is low, there is certain anti-flammability, it is easy to process, suitable for glass fibre and its
Its filler filling enhancing modified, improve performance and expand application.PA's is various in style, have PA6, PA66, PAll, PAl2,
PA46, PA610, PA612, PAl010 etc., and the semi-aromatic nylon PA6T developed in recent years and extraordinary nylon etc. are many new
Kind.PA plastics are with a long history, widely used general engineering plastics.World's engineering plastics marketing sharing in 2000 is PA
35%th, PC 32%, POM 11%, PBT 10%, PPO 3%, PET 2%, UHMWPE 2%, high performance engineering plastics (PPS polyamide,
LCP, PEEK, PEI, PESU, PVDF, other fluoro-containing plastics etc.）2%.
The problem of foaming of current nylon is faced as polypropylene --- melt strength is low, and too low melt strength is difficult bag
Firmly gas, foamed gas are easily escaped, and foaming process is difficult control, easily cause steep that wall rupture in foaming process, gas escape, bubble
Hole caves in and bubble merges.
The content of the invention
The defects of melt strength is low, bubble easily caves in be present for nylon foaming, the present invention proposes one kind with gel state
The method of nylon blown foams.Its significant advantage is the nylon that foamed under the conditions of gel state, has been got around in common method
Under molten state the problem of nylon melt low intensity, and step is succinct, and operation is easy, is adapted to large-scale production.
To solve the above problems, the present invention uses following technical scheme：
A kind of method with gel state nylon blown foams, it is characterised in that shown in comprising the following steps that：
1）Formamide, methanol, ethanol are mixed by weight；
2）By step 1）Metal salt is added in the solution mixed, is stirred under air-proof condition, obtains colloidal sol；
3）By step 2）Obtained colloidal sol heated sealed, add polyisobutene and be ultrasonically treated, at room temperature sealing and standing, you can obtain
Nylon gel body；
4）Antioxidant, foam stabilizer are added again and are stirred；
5）Quick pressure releasing is foamed after injection supercritical gas, then steam-cured in the catalyst to obtain foamed plastics.
Above-mentioned raw material coordinates according to parts by weight：Formamide 50-70 parts, methanol 24-36 parts, ethanol 21-27 parts, metal salt
13-17 parts, polyisobutene 3-5 parts, foam stabilizer 7-10 parts, antioxidant 4-8 parts.
The foam stabilizer is polyurethane foams stabilizers.
The antioxidant is polyolefin, polyformaldehyde according to mass ratio 1:4 mix.
One kind in the metal salt sodium chloride, potassium chloride, calcium chloride.
Described polyisobutene selects molecular weight 1000-3000 thick gel.
One or more of the described catalyst in hypophosphite, phosphate, ortho phosphorous acid, phosphoric acid or phosphate
Dilution.Further, the step 3）The time control of middle supersound process is in 10-20min.
A kind of method with gel state nylon blown foams of the invention, it is by metal salt, polyisobutene that nylon is pre-
Polymer gels state, then foams, and further makes its polymerization-stable using catalyst is steam-cured, forms foamed plastics.This method gram
The defects of nylon directly heats foamed melt slightly low foam wall is easily caved in is taken.Obtained foam not only uniform foam cell, and
And light intensity is high, technical support is provided to develop the application of nylon foam.
A kind of method with gel state nylon blown foams of the invention, compared with prior art, the characteristics of it is protruded
It is with excellent effect：
1st, metal salt being mixed with formamide, methanol, the mixed solution of ethanol, the addition of metal salt obtains nylon gel body,
And the control to nylon crystallinity can be realized, nylon state of aggregation control technology is more perfect, and is made by introducing polyisobutene
Obtained nylon gel body is easy to foam.
2nd, got around in common method under molten state the problem of nylon melt low intensity, nylon melt intensity enhancing encases hair
Gas caused by infusion, foamed gas are not easy to escape, and foaming process can control, and do not easily cause steep that wall rupture, gas in foaming process
Body escape, abscess are caved in and bubble merges.Further enhance the intensity of nylon.
3rd, the inventive method prepares nylon foaming, and input is small, cost is low, non-environmental-pollution, yield are high, has significant city
Field application value.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of method with gel state nylon blown foams, it is characterised in that shown in comprising the following steps that：(raw material with
Parts by weight meter)
1）By 21 parts of 50 parts of formamide, 24 parts of methanol, ethanol mixing；
2）By step 1）13 parts of metal salt sodium chloride is added in the solution mixed, is stirred under air-proof condition, obtains colloidal sol；
3）By step 2）Obtained colloidal sol heated sealed, add molecular weight 1000-3000 5 parts of supersound process of polyisobutene
10min, at room temperature sealing and standing, you can obtain nylon gel body；
4）4 parts of antioxidant, 7 parts of foam stabilizer are added again, and are stirred；The antioxidant be polyolefin, polyformaldehyde according to
Mass ratio 1:4 mix;The foam stabilizer is polyurethane foams stabilizers；
5）Quick pressure releasing is foamed after injection supercritical gas, then steam-cured in the dilution of catalyst phosphite to obtain
Foamed plastics.
Obtained foam is tested, as shown in table 1, it shows as good compressive strength, uniform abscess, compares
There is significant advantage in the nylon foamed plastics of conventional hot melt foaming.
Embodiment 2
A kind of method with gel state nylon blown foams, it is characterised in that shown in comprising the following steps that：(raw material with
Parts by weight meter)
1）By 25 parts of 60 parts of formamide, 30 parts of methanol, ethanol mixing；
2）By step 1）17 parts of metal salt potassium chloride is added in the solution mixed, is stirred under air-proof condition, obtains colloidal sol；
3）By step 2）Obtained colloidal sol heated sealed, add molecular weight 1000-3000 3 parts of supersound process of polyisobutene
20min, at room temperature sealing and standing, you can obtain nylon gel body；
4）5 parts of antioxidant, 7 parts of foam stabilizer are added again, and are stirred；The antioxidant be polyolefin, polyformaldehyde according to
Mass ratio 1:4 mix;The foam stabilizer is polyurethane foams stabilizers；
5）Quick pressure releasing is foamed after injection supercritical gas, then steam-cured in the dilution of catalyst phosphoric acid to obtain foam
Plastics.
Obtained foam is tested, as shown in table 1, it shows as good compressive strength, uniform abscess, compares
There is significant advantage in the nylon foamed plastics of conventional hot melt foaming.
Embodiment 3
A kind of method with gel state nylon blown foams, it is characterised in that shown in comprising the following steps that：(raw material with
Parts by weight meter)
1）By 21 parts of 70 parts of formamide, 24 parts of methanol, ethanol mixing；
2）By step 1）17 parts of metal salt is added in the solution mixed, is stirred under air-proof condition, obtains colloidal sol；
3）By step 2）Obtained colloidal sol heated sealed, add molecular weight 1000-3000 5 parts of supersound process of polyisobutene
15min, at room temperature sealing and standing, you can obtain nylon gel body；
4）8 parts of antioxidant, 10 parts of foam stabilizer are added again, and are stirred；The antioxidant be polyolefin, polyformaldehyde according to
Mass ratio 1:4 mix;The foam stabilizer is polyurethane foams stabilizers；
5）Quick pressure releasing is foamed after injection supercritical gas, then steam-cured in the dilution of catalyst phosphate to be steeped
Foam plastics.
Obtained foam is tested, as shown in table 1, it shows as good compressive strength, with uniform with literary east
Abscess, there is significant advantage compared to the nylon foamed plastics of conventional hot melt foaming.
Embodiment 4
A kind of method with gel state nylon blown foams, it is characterised in that shown in comprising the following steps that：(raw material with
Parts by weight meter)
1）By 27 parts of 50 parts of formamide, 36 parts of methanol, ethanol mixing；
2）By step 1）13 parts of metal salt sodium chloride is added in the solution mixed, is stirred under air-proof condition, obtains colloidal sol；
3）By step 2）Obtained colloidal sol heated sealed, add molecular weight 1000-3000 5 parts of supersound process of polyisobutene
20min, at room temperature sealing and standing, you can obtain nylon gel body；
4）8 parts of antioxidant, 10 parts of foam stabilizer are added again, and are stirred；The antioxidant be polyolefin, polyformaldehyde according to
Mass ratio 1:4 mix;The foam stabilizer is polyurethane foams stabilizers；
5）Quick pressure releasing is foamed after injection supercritical gas, then steam-cured in the dilution of catalyst ortho phosphorous acid to obtain
Foamed plastics.
Obtained foam is tested, as shown in table 1, it shows as good compressive strength, with uniform with literary east
Abscess, there is significant advantage compared to the nylon foamed plastics of conventional hot melt foaming.
Embodiment 5
A kind of method with gel state nylon blown foams, it is characterised in that shown in comprising the following steps that：(raw material with
Parts by weight meter)
1）By 21 parts of 55 parts of formamide, 24 parts of methanol, ethanol mixing；
2）By step 1）15 parts of metal salt sodium chloride is added in the solution mixed, is stirred under air-proof condition, obtains colloidal sol；
3）By step 2）Obtained colloidal sol heated sealed, add molecular weight 1000-3000 5 parts of supersound process of polyisobutene
20min, at room temperature sealing and standing, you can obtain nylon gel body；
4）5 parts of antioxidant, 8 parts of foam stabilizer are added again, and are stirred；The antioxidant be polyolefin, polyformaldehyde according to
Mass ratio 1:4 mix;The foam stabilizer is polyurethane foams stabilizers；
5）Quick pressure releasing is foamed after injection supercritical gas, then steam-cured in the dilution of catalyst phosphite to obtain
Foamed plastics.
Obtained foam is tested, as shown in table 1, it shows as good compressive strength, with uniform with literary east
Abscess, there is significant advantage compared to the nylon foamed plastics of conventional hot melt foaming.
Embodiment 6
A kind of method with gel state nylon blown foams, it is characterised in that shown in comprising the following steps that：(raw material with
Parts by weight meter)
1）By 21 parts of 70 parts of formamide, 24 parts of methanol, ethanol mixing；
2）By step 1）13 parts of metal salt calcium chloride is added in the solution mixed, is stirred under air-proof condition, obtains colloidal sol；
3）By step 2）Obtained colloidal sol heated sealed, add molecular weight 1000-3000 4 parts of supersound process of polyisobutene
10min, at room temperature sealing and standing, you can obtain nylon gel body；
4）8 parts of antioxidant, 7 parts of foam stabilizer are added again, and are stirred；The antioxidant be polyolefin, polyformaldehyde according to
Mass ratio 1:4 mix;The foam stabilizer is polyurethane foams stabilizers；
5）Quick pressure releasing is foamed after injection supercritical gas, then steam-cured in the dilution of catalyst phosphoric acid to obtain foam
Plastics.
Obtained foam is tested, as shown in table 1, it shows as good compressive strength, with uniform with literary east
Abscess, there is significant advantage compared to the nylon foamed plastics of conventional hot melt foaming.
Table 1：
| Embodiment | Compressive strength（MPa） | Dimensional stability | Density（kg/m3） |
| Embodiment 1 | 0.65 | ＜ 0.5% | 23.7 |
| Embodiment 2 | 0.64 | ＜ 0.5% | 21.2 |
| Embodiment 3 | 0.61 | ＜ 0.5% | 21.8 |
| Embodiment 4 | 0.63 | ＜ 0.5% | 22.7 |
| Embodiment 5 | 0.64 | ＜ 0.5% | 25.7 |
| Embodiment 6 | 0.65 | ＜ 0.5% | 26.9 |
| Heat the nylon foam of foaming | 0.15 | ＜ 5% | 51.6 |
But nylon, its compressive strength are only 0 under molten state in traditional common method:Below 15MPa, metal salt is different with gathering
The nylon gel body that butylene makes to obtain is easy to foam, and can realize the control to nylon crystallinity, nylon state of aggregation control skill
Art is more perfect.Get around in common method under molten state the problem of nylon melt low intensity, strengthened the intensity of nylon.The present invention
Method prepares nylon foaming, and input is small, cost is low, non-environmental-pollution, yield are high, has significant market application value.
Claims (7)
- A kind of 1. method with gel state nylon blown foams, it is characterised in that shown in comprising the following steps that：1）Formamide, methanol, ethanol are mixed by weight；2）By step 1）Metal salt is added in the solution mixed, is stirred under air-proof condition, obtains colloidal sol；3）By step 2）Obtained colloidal sol heated sealed, add polyisobutene and be ultrasonically treated, at room temperature sealing and standing, you can obtain Nylon gel body；4）Antioxidant, foam stabilizer are added again and are stirred；5）Quick pressure releasing is foamed after injection supercritical gas, then steam-cured in the catalyst to obtain foamed plastics；Above-mentioned raw material coordinates according to parts by weight：Formamide 50-70 parts, methanol 24-36 parts, ethanol 21-27 parts, metal salt 13- 17 parts, polyisobutene 3-5 parts, foam stabilizer 7-10 parts, antioxidant 4-8 parts.
- A kind of 2. method with gel state nylon blown foams according to claim 1, it is characterised in that：The even bubble Agent is polyurethane foams stabilizers.
- A kind of 3. method with gel state nylon blown foams according to claim 1, it is characterised in that：The antioxygen Agent is polyolefin, polyformaldehyde according to mass ratio 1:4 mix.
- A kind of 4. method with gel state nylon blown foams according to claim 1, it is characterised in that：The metal One kind in salt sodium chloride, potassium chloride, calcium chloride.
- A kind of 5. method with gel state nylon blown foams according to claim 1, it is characterised in that：Described is poly- Isobutene selects molecular weight 1000-3000 thick gel.
- A kind of 6. method with gel state nylon blown foams according to claim 1, it is characterised in that：Described urges One or more of dilutions of the agent in hypophosphite, phosphate, ortho phosphorous acid, phosphoric acid or phosphate.
- A kind of 7. method with gel state nylon blown foams according to claim 1, it is characterised in that：Step 3）In The time control of supersound process is in 10-20min.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110417584.2A CN113045890A (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
| CN202110418399.5A CN112961494A (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
| CN201710727606.9A CN107501594B (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710727606.9A CN107501594B (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110418399.5A Division CN112961494A (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
| CN202110417584.2A Division CN113045890A (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
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| CN107501594A true CN107501594A (en) | 2017-12-22 |
| CN107501594B CN107501594B (en) | 2021-05-25 |
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| CN201710727606.9A Active CN107501594B (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
| CN202110417584.2A Withdrawn CN113045890A (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
| CN202110418399.5A Withdrawn CN112961494A (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
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| CN202110417584.2A Withdrawn CN113045890A (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
| CN202110418399.5A Withdrawn CN112961494A (en) | 2017-08-23 | 2017-08-23 | Method for foaming foamed plastic by using gel state nylon |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527081A (en) * | 2019-08-30 | 2019-12-03 | 华侨大学 | A kind of preparation method and applications of surfactant-free foam in place MCPA6 |
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- 2017-08-23 CN CN202110417584.2A patent/CN113045890A/en not_active Withdrawn
- 2017-08-23 CN CN202110418399.5A patent/CN112961494A/en not_active Withdrawn
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527081A (en) * | 2019-08-30 | 2019-12-03 | 华侨大学 | A kind of preparation method and applications of surfactant-free foam in place MCPA6 |
| CN110527081B (en) * | 2019-08-30 | 2022-03-04 | 华侨大学 | Preparation method and application of surfactant-free in-situ foaming MCPA6 |
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| CN113045890A (en) | 2021-06-29 |
| CN107501594B (en) | 2021-05-25 |
| CN112961494A (en) | 2021-06-15 |
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