CN102924744A - Modified polymer foam material and preparation method for same - Google Patents
Modified polymer foam material and preparation method for same Download PDFInfo
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- CN102924744A CN102924744A CN2012104883279A CN201210488327A CN102924744A CN 102924744 A CN102924744 A CN 102924744A CN 2012104883279 A CN2012104883279 A CN 2012104883279A CN 201210488327 A CN201210488327 A CN 201210488327A CN 102924744 A CN102924744 A CN 102924744A
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Abstract
The invention provides a modified polymer foam material and a preparation method for the same. The method comprises the following steps of: in the presence of a dehydrating agent and an acylation catalyst, performing substitution reaction on C1-C22 aliphatic monoacyl chloride or C7-C20 aromatic monoacyl chloride and a polyvinyl acetal foam material having an apparent density of 0.04-0.09 g/cm<3> and a water absorptivity of 1800-2800% in an organic solvent at 25-150 DEG C, reacting for 1-170 hours, and then obtaining the modified polymer foam material. According to the invention, the reaction conditions such as the temperature and the time are controlled to completely substitute hydroxyl in the polyvinyl acetal foam material, so that the hydrophilicity of the polyvinyl acetal foam material is obviously reduced, and lipophilicity is given to the polyvinyl acetal foam material; and the polyvinyl acetal foam material is good in mechanical property, and capable of guaranteeing maintenance for the open pore structure thereof after modification with the conditions aforementioned, so that the modified polymer foam material is rapid in oil absorption, high in oil absorption amount and high in application value.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly a kind of polymer-modified foam materials and preparation method thereof.
Background technology
In recent years, along with the fast development of economy, the leakage of oil event takes place frequently, and a large amount of organic carbon hydrogen compounds flows into water body, has caused serious harm for the ecotope of ocean and human living environment, and therefore, how in time processing these pollutents becomes urgent problem.At present, the material of some types has been applied to the processing of these pollutents in the water as comprising dispersion agent, sinking agent, jelling agent, incendiary material, biodegradation agent and the oil absorber etc. of Corexit 9500 that Naclo produces and Corexit 9527 etc.Wherein, because oil absorber or oil absorption material can collect oil and separate from water, its application has caused people's extensive concern.
According to forming and the source, oil absorption material can be divided into inorganic oil absorption material, natural oil absorption material and synthetic macromolecule oil absorption material.Wherein, inorganic oil absorption material such as clay and zeolite etc., itself do not have the very weak (M.O.Adebajo of oil absorptiveness or oil absorptiveness, R.L.Frost, et al.Journal of Porous Materials 10:159-170,2003), although can connect hydrophobic group to improve its oil absorptiveness at inorganic material surface, but for gel-type and the inorganic oil absorption material of multi-hole type, its oil number lower (O.K.Karakasi, A.Moutsatsou.Fuel 89(2010) 3966-3970).Natural macromolecular material such as corn stalk (M.Husseien, A.A.Amer, et al.J.Anal.Appl.Pyrolysis 86(2009) 360-363), cotton, bombax cotton, silkweed (R.S.Rengasamy, D.Das, et al.Journal of Hazardous Materials 186(2011) 526-532) etc., owing to have renewable, wide material sources and be rich in the characteristics such as reactive functionality, can modify by surface hydrophobicity and have certain oil absorptiveness, but still there is the not high problem of oil number (G Deschamps, et al.Environ.Sci.Technol.2003.37.1013-1015), its biodegradable characteristic is so that this class material is difficult to the long time stored (D.Ceylan for subsequent use of conduct prevention material simultaneously, S.Dogu, et al.Environ.Sci.Technol, 43(2009), 3846-3852).Common synthetic macromolecule oil absorption material mainly is oil-absorbing resin, such as the gel-type oil-absorbing resin, it is normally by long-chain acrylate and the diene crosslinking copolymerization obtains as Vinylstyrene (DVB) product (Xiao-Ming Zhou, Cheng Zhi Chuai, Journal of Applied Polymer Science, Vol.115(2010), 3321-3325), have preferably hydrophobic performance and absorption property, but swelling rate is low, is difficult to the demand of solution of emergent event.
And hydrophobic type polymkeric substance non-woven material can remedy the deficiency of the low swelling rate of above-mentioned gel-type oil-absorbing resin, such as the present polypropylene-base oil absorption material that comprises oil absorbent material, oil sucting pad and oil suction rope etc. of the marketization, diameter, hole size and oil property according to non-woven fibre are different, it is saturated that it generally can just can reach absorption to dozens of minutes fast at several minutes, but, this class polypropylene-base oil absorption material is still lower on absorbed dose, generally can not be higher than 15g/g, this has limited its application to a great extent.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of polymer-modified foam materials and preparation method thereof, the polymer-modified foam materials of the method preparation has high swelling rate and high oil number, and using value is larger.
The invention provides a kind of preparation method of polymer-modified foam materials, may further comprise the steps:
In the presence of dewatering agent and acylation catalyst, polyvinyl acetal foam materials and acyl chlorides are carried out substitution reaction in 25 ℃ ~ 150 ℃ in organic solvent, react after 1 hour ~ 170 hours, obtain polymer-modified foam materials;
The apparent density of described polyvinyl acetal foam materials is 0.04g/cm
3~ 0.09g/cm
3, and water-intake rate is 1800% ~ 2800%; Described acyl chlorides is C
1~ C
22Aliphatics monobasic acyl chlorides or C
7~ C
20Aromatic series monobasic acyl chlorides.
Preferably, the mass ratio of described polyvinyl acetal foam materials and acyl chlorides is 2:5 ~ 20.
Preferably, described acylation catalyst is pyridine, DMAP, diethylamine or triethylamine.
Preferably, the mass ratio of described acylation catalyst and polyvinyl acetal foam materials is 0.2 ~ 0.8:2.
Preferably, described dewatering agent is 4A level molecular sieve, silica gel, anhydrous magnesium sulfate, anhydrous calciumsulphate or anhydrous sodium sulphate.
Preferably, the mass ratio of described dewatering agent and polyvinyl acetal foam materials is 8 ~ 15:2.
Preferably, described organic solvent is one or more in dimethyl sulfoxide (DMSO), dimethyl formamide, acetonitrile and the N-Methyl pyrrolidone.
Preferably, described organic solvent is one or more in toluene, dimethylbenzene, chlorobenzene and the tetracol phenixin.
Preferably, the mass ratio of the volume of described organic solvent and polyvinyl acetal foam materials is (80 ~ 150) mL:2g.
The polymer-modified foam materials that the present invention also provides a kind of preparation method by mentioned earlier to make.
Compared with prior art, the present invention is with C
1~ C
22Aliphatics monobasic acyl chlorides or C
7~ C
20Aromatic series monobasic acyl chlorides, dewatering agent, acylation catalyst, organic solvent and apparent density are 0.04g/cm
3~ 0.09g/cm
3And water-intake rate is that 1800% ~ 2800% polyvinyl acetal foam materials mixes, and in temperature is under 25 ℃ ~ 150 ℃ the condition substitution reaction to occur, and reacts after 1 hour ~ 170 hours, obtains polymer-modified foam materials.The present invention is take apparent density as 0.04g/cm
3~ 0.09g/cm
3And water-intake rate is that 1800% ~ 2800% polyvinyl acetal foam materials is precursor, take organic solvent as reaction medium, under the effect of dewatering agent and acylation catalyst, with C
1~ C
22Aliphatics monobasic acyl chlorides or C
7~ C
20Aromatic series monobasic acyl chlorides is modifying agent, and described precursor is carried out hydrophobically modified, and the present invention controls the reaction conditionss such as said temperature and time, hydroxyl in the polyvinyl acetal foam materials is replaced fully and obviously reduces its wetting ability, gives its lipophilicity; Simultaneously, described polyvinyl acetal foam materials itself has good mechanical property, can guarantee that its open-celled structure is kept after the modification of above-mentioned condition, the actings in conjunction such as above-mentioned modifying agent and precursor, thus make the polymer-modified foam materials that makes have quick and efficient oil suction characteristics.Experimental result shows that the time that the polymer-modified foam materials of method preparation provided by the invention reaches the oil product saturated absorption can only need 2s, and absorbency is generally more than 20g/g.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The invention provides a kind of preparation method of polymer-modified foam materials, may further comprise the steps:
In the presence of dewatering agent and acylation catalyst, polyvinyl acetal foam materials and acyl chlorides are carried out substitution reaction in 25 ℃ ~ 150 ℃ in organic solvent, react after 1 hour ~ 170 hours, obtain polymer-modified foam materials;
The apparent density of described polyvinyl acetal foam materials is 0.04g/cm
3~ 0.09g/cm
3, and water-intake rate is 1800% ~ 2800%; Described acyl chlorides is C
1~ C
22Aliphatics monobasic acyl chlorides or C
7~ C
20Aromatic series monobasic acyl chlorides.
The present invention carries out substitution reaction after polyvinyl acetal foam materials, acyl chlorides, dewatering agent, acylation catalyst and organic solvent are mixed in reactor; the temperature of reaction is 25 ℃ ~ 150 ℃; the time of reaction is 1 hour ~ 170 hours, obtains polymer-modified foam materials.
The present invention is take the polyvinyl acetal foam materials as precursor, it is the polymer materials with a large amount of pore structures that polyvinyl alcohol solution obtains under pore former, emulsifying agent and linking agent acting in conjunction, wherein, described linking agent can be in formaldehyde, Paraformaldehyde 96 and the dialdehyde one or more, also can for Epicholorohydrin, diprotic acid, dibasic acid anhydride, polyprotonic acid, multi-anhydride, binary isocyanic ester or multicomponent isocyanate etc. can with bifunctional or the polyfunctional compound of hydroxyl reaction; Have the oxygen attack aldehyde carbonyl under acid catalysis on the hydroxyl of strong nucleation in the described polyvinyl alcohol, form unsettled hemiacetal, it further forms acetal with adjacent alcohol effect again.
In the present invention, described polyvinyl acetal foam materials is the open cell type material, and apparent density is 0.04g/cm
3~ 0.09g/cm
3, and water-intake rate is 1800% ~ 2800%, has good mechanical property and higher percentage of open area, and efficient, this is one of prerequisite that makes the rapidly and efficiently oil suction of polymer-modified foam materials to water absorbing properties fast.The apparent density of described polyvinyl acetal foam materials is preferably 0.06g/cm
3~ 0.08g/cm
3The water-intake rate of described polyvinyl acetal foam materials is preferably 2300% ~ 2600%.
The measuring method of the water-intake rate of described polyvinyl acetal foam materials is as follows:
Measure the initial weight of a certain size polyvinyl acetal foam sample, be denoted as A, then this sample was soaked in distilled water 10 minutes, sample after take out soaking is placed on filter 23 0s on the filtering net, weighs after removing its surperficial water, be denoted as B, calculate according to formula (1) again, get the mean value of 3 observed values, as the water-intake rate of described polyvinyl acetal foam materials.
The present invention does not have particular restriction to the source of described polyvinyl acetal foam materials, can buy from the market, can be that the preparation method of the disclosed polyvinyl acetal base of the Chinese patent literature foam materials of CN101507826A makes according to publication number also:
Be that 4% ~ 8% polyvinyl alcohol, 65% ~ 75% water, 1% ~ 4% aldehyde, 1% ~ 2% tensio-active agent and 1% ~ 2% pore former mix the liquid that obtains mixing with mass percent; With this liquid pour in the agitator stir 10 minutes ~ 30 minutes after, the adding mass percent is 15% ~ 25% acid, continue to stir 20 minutes ~ 40 minutes, pour into again in the acidproof mould, be to be cured typing under 30 ℃ ~ 60 ℃ the condition in temperature, after 4 hours ~ 40 hours, through washing, drying, obtain target product;
Described polyvinyl alcohol alcoholysis degree is greater than 88%, and the polymerization degree is 1500 ~ 2000; Described aldehyde is formaldehyde, Paraformaldehyde 96 or their mixture; Described acid is sulfuric acid or phosphoric acid; Described tensio-active agent can be sodium lauryl sulphate, sodium laurylsulfonate or sodium dibutyl naphthalene sulfonate, also can be in polyoxyethylene 20 sorbitan monolaurate, polyoxyethylene 20 sorbitan monopalmitate, polyoxyethylene 20 sorbitan monostearate and the polyoxyethylene 20 sorbitan monooleate one or more; Described pore former is yam starch or W-Gum.
The present invention is take acyl chlorides as modifying agent, and described acyl chlorides is C
1~ C
22Aliphatics monobasic acyl chlorides or C
7~ C
20Aromatic series monobasic acyl chlorides; with Sauerstoffatom generation acylation reaction in the described polyvinyl acetal foam materials; hydroxyl hydrogen atom is replaced by acyl group and generate ester, that is, hydroxyl hydrogen atom is had the oleophylic performance by hydrophobic acyl substituted in the hydrophilic polyvinyl acetal foam materials.Described acyl chlorides can be saturated or undersaturated C
1~ C
22Aliphatics monobasic acyl chlorides is preferably C
5~ C
20Aliphatics monobasic acyl chlorides, more preferably C
10~ C
18Aliphatics monobasic acyl chlorides most preferably is stearyl chloride (C
18), lauroyl chloride (C
12), palmityl chloride (C
16) or the hendecene acyl chlorides; Described acyl chlorides can be saturated or undersaturated C
7~ C
20Aromatic series monobasic acyl chlorides is preferably C
8~ C
18Aromatic series monobasic acyl chlorides, more preferably benzene butyryl chloride or Benzoyl chloride.
Substitution reaction occurs in described polyvinyl acetal foam materials and described acyl chlorides in organic solvent under the effect of dewatering agent and acylation catalyst.The mass ratio of described polyvinyl acetal foam materials and described acyl chlorides is preferably 2:5 ~ 20, more preferably 2:8 ~ 15;
Described acylation catalyst is preferably pyridine compounds and their, diethylamine or triethylamine, more preferably pyridine, DMAP, diethylamine or triethylamine; The mass ratio of described acylation catalyst and described polyvinyl acetal foam materials is preferably 0.2 ~ 0.8:2, more preferably 0.3 ~ 0.6:2;
Described dewatering agent is preferably 4A level molecular sieve, silica gel, anhydrous magnesium sulfate, anhydrous calciumsulphate or anhydrous sodium sulphate; Wherein, described silica gel is preferably dry silica gel; The mass ratio of described dewatering agent and described polyvinyl acetal foam materials is preferably 8 ~ 15:2, more preferably 9 ~ 12:2;
Described organic solvent can be the larger organic solvent of polarity, is preferably one or more in dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), acetonitrile and the N-Methyl pyrrolidone (NMP); Described organic solvent also can for the less organic solvent of polarity, be preferably one or more in toluene, dimethylbenzene, chlorobenzene and the tetracol phenixin; The mass ratio of the volume of described organic solvent and described polyvinyl acetal foam materials is preferably (80 ~ 150) mL:2g, more preferably (90 ~ 120) mL:2g.
Above-mentioned material is reaction 1 hour ~ 170 hours under 25 ℃ ~ 150 ℃ the condition in temperature, hydroxyl in the described polyvinyl acetal foam materials is replaced fully and obviously reduces its wetting ability, gives its lipophilicity, obtains polymer-modified foam materials after the drying; Simultaneously, described polyvinyl acetal foam materials itself has good mechanical property, can guarantee that its open-celled structure is kept after the modification of above-mentioned condition, thereby makes the polymer-modified foam materials that makes have quick and efficient oil absorptiveness.
The temperature of described reaction is preferably 30 ℃ ~ 120 ℃; The time of described reaction is preferably 5 hours ~ and 150 hours.Preparation method's preparation condition provided by the invention is gentle, and technique is simple, is suitable for large-scale industrial production.
The polymer-modified foam materials that the present invention also provides a kind of preparation method by mentioned earlier to make.
After obtaining polymer-modified foam materials, the present invention carries out oil absorptiveness to it and measures.In the present invention, measure the initial weight of a certain size polymer-modified foam sample, be denoted as A, then this sample is placed oil product such as normal hexane, kerosene, whiteruss, toluene or tetracol phenixin, soak 0.5min, 30min(0.5h), 150min(2.5h), 900min(15h), 1440min(24h), 2880min(48h) or 4320min(72h), when its weight no longer changes or change hour, the time that record soaks, obtain the oil suction saturation time; Then take out the sample after soaking, be placed on and filter 0.5min on the filtering net, weigh behind the oil on its surface of elimination, be denoted as B, calculate according to formula (1) again, get the mean value of 3 observed values, obtain oil absorbency and the absorbency of the polymer-modified foam materials of gained;
Oil absorbency (%)=(B-A)/A(absorbency) * 100%(1);
The sample that above-mentioned oil suction is reached capacity is by simple extruding well known to those skilled in the art, weigh after removing most oil, be denoted as C, calculate according to formula (2) again, get the mean value of 25 observed values, obtain the Oil Recovery rate of the polymer-modified foam materials of gained;
Oil Recovery rate (%)=1-(C-A)/(B-A) * 100%(2).
Measurement result shows that the time that the polymer-modified foam materials of the method preparation that the embodiment of the invention provides reaches the oil product saturated absorption can only need 2s, except density is 0.6594g/cm
3Normal hexane beyond, generally more than 20g/g, the Oil Recovery rate is more than 80% for absorbency.The polymer-modified foam materials that shows method preparation provided by the invention has preferably absorptive character to various oil products, and swelling rate is fast and oil number is high.
In addition, the polymer-modified foam materials of method preparation provided by the invention has good rebound performance and mechanical property, only needs just can realize absorbing the recovery of oil product and reusing of oil absorption material by simple extruding.And the preparation method of polymer-modified foam materials provided by the invention is simple and easy to do, is suitable for suitability for industrialized production.
In order further to understand the present invention, below in conjunction with embodiment polymer-modified foam materials provided by the invention and preparation method thereof is specifically described.
Embodiment 1
With the 100g polymerization degree be 1500, alcoholysis degree is that 98% polyvinyl alcohol is dissolved in that to be made into mass percent in the 900g hot water be 10% solution, to wherein adding 10g polyoxyethylene 20 sorbitan monolaurate, 10g Sodium dodecylbenzene sulfonate, 65mL formaldehyde and 25g yam starch, pour into after mixing in the agitator, stirred 20 minutes; Be 50% sulfuric acid to wherein adding the 500mL mass percent again, continue to stir after 20 minutes, pour the liquid of described stirring into acidproof mould, put into thermostat container, at 24 hours curing moldings of 40 ℃ of lower reactions, through washing, drying, obtain the polyvinyl acetal foam materials, its apparent density is 0.051g/cm
3, water-intake rate is 2800%.
Embodiment 2
The polyvinyl acetal foam materials, 10g4A level molecular sieve, 100mL toluene, 0.5mL pyridine and the 5g stearyl chloride that in the clean round-bottomed flask of 250mL, add 2g embodiment 1 preparation, at 25 ℃ of lower reaction 170h, drying obtains polymer-modified foam materials.
Get the polymer-modified foam materials that 0.1g obtains, respectively according to method mensuration mentioned above saturated absorption time, absorbency and Oil Recovery rate to kerosene.Measurement result shows that its saturated absorption time is 5s, and absorbency is 24g/g, and the Oil Recovery rate is 91.0%.
Embodiment 3
The polyvinyl acetal foam materials, 10g anhydrous magnesium sulfate, 100mL acetonitrile, 0.5mL triethylamine and the 20g lauroyl chloride that in the clean round-bottomed flask of 250mL, add 2g embodiment 1 preparation, at 40 ℃ of lower reaction 80h, drying obtains polymer-modified foam materials.
Get the polymer-modified foam materials that 0.1g obtains, respectively according to method mensuration mentioned above saturated absorption time, absorbency and Oil Recovery rate to normal hexane.Measurement result shows that its saturated absorption time is 2s, and absorbency is 17g/g, and the Oil Recovery rate is 92.4%.
Embodiment 4
The polyvinyl acetal foam materials, 10g anhydrous calciumsulphate, 100mLDMF, 0.5g4-Dimethylamino pyridine and the 5g benzene butyryl chloride that in the clean round-bottomed flask of 250mL, add 2g embodiment 1 preparation, at 60 ℃ of lower reaction 60h, drying obtains polymer-modified foam materials.
Get the polymer-modified foam materials that 0.1g obtains, respectively according to method mensuration mentioned above saturated absorption time, absorbency and Oil Recovery rate to whiteruss.Measurement result shows that its saturated absorption time is 10min, and absorbency is 21g/g, and the Oil Recovery rate is 84.2%.
Embodiment 5
The polyvinyl acetal foam materials, 10g dry silica gel, 100mLDMSO, 0.5mL pyridine and the 5g benzene butyryl chloride that add 2g embodiment 1 preparation in the clean round-bottomed flask of 250mL, at 80 ℃ of lower reaction 40h, drying obtains polymer-modified foam materials.
Get the polymer-modified foam materials that 0.1g obtains, respectively according to method mensuration mentioned above saturated absorption time, absorbency and Oil Recovery rate to hydraulic efficiency oil.Measurement result shows that its saturated absorption time is 10min, and absorbency is 20g/g, and the Oil Recovery rate is 83.5%.
Embodiment 6
The polyvinyl acetal foam materials, 10g anhydrous sodium sulphate, 100mL toluene, 0.5mL diethylamine and the 6g Benzoyl chloride that in the clean round-bottomed flask of 250mL, add 2g embodiment 1 preparation, at 100 ℃ of lower back flow reaction 30h, drying obtains polymer-modified foam materials.
Get the polymer-modified foam materials that 0.1g obtains, respectively according to method mensuration mentioned above saturated absorption time, absorbency and Oil Recovery rate to normal hexane.Measurement result shows that its saturated absorption time is 5s, and absorbency is 16g/g, and the Oil Recovery rate is 91.5%.
Embodiment 7
The polyvinyl acetal foam materials, 10g dry silica gel, 100mL toluene, 0.5mL diethylamine and the 10g hendecene acyl chlorides that in the clean round-bottomed flask of 250mL, add 2g embodiment 1 preparation, at 150 ℃ of lower back flow reaction 10h, drying obtains polymer-modified foam materials.
Get the polymer-modified foam materials that 0.1g obtains, respectively according to method mensuration mentioned above saturated absorption time, absorbency and Oil Recovery rate to vegetables oil.Measurement result shows that its saturated absorption time is 20min, and absorbency is 21g/g, and the Oil Recovery rate is 85.7%.
Embodiment 8
The polyvinyl acetal foam materials, 10g4A level molecular sieve, 100mL toluene, 0.5mL diethylamine and the 15g palmityl chloride that in the clean round-bottomed flask of 250mL, add 2g embodiment 1 preparation, at 150 ℃ of lower back flow reaction 6h, drying obtains polymer-modified foam materials.
Get the polymer-modified foam materials that 0.1g obtains, respectively according to method mensuration mentioned above saturated absorption time, absorbency and Oil Recovery rate to whiteruss.Measurement result shows that its saturated absorption time is 11min, and absorbency is 20g/g, and the Oil Recovery rate is 85.0%.
As seen from the above embodiment, the time that the polymer-modified foam materials of the method preparation that the embodiment of the invention provides reaches the oil product saturated absorption can only need 2s, except density is 0.6594g/cm
3Normal hexane beyond, generally more than 20g/g, the Oil Recovery rate is more than 80% for absorbency.The polymer-modified foam materials that shows method preparation provided by the invention has preferably absorptive character to various oil products, and swelling rate is fast and oil number is high.
In addition, the polymer-modified foam materials of method preparation provided by the invention has good rebound performance and mechanical property, only needs just can realize absorbing the recovery of oil product and reusing of oil absorption material by simple extruding.And the preparation method of polymer-modified foam materials provided by the invention is simple and easy to do, is suitable for suitability for industrialized production.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of a polymer-modified foam materials may further comprise the steps:
In the presence of dewatering agent and acylation catalyst, polyvinyl acetal foam materials and acyl chlorides are carried out substitution reaction in 25 ℃ ~ 150 ℃ in organic solvent, react after 1 hour ~ 170 hours, obtain polymer-modified foam materials;
The apparent density of described polyvinyl acetal foam materials is 0.04g/cm
3~ 0.09g/cm
3, and water-intake rate is 1800% ~ 2800%; Described acyl chlorides is C
1~ C
22Aliphatics monobasic acyl chlorides or C
7~ C
20Aromatic series monobasic acyl chlorides.
2. preparation method according to claim 1 is characterized in that, the mass ratio of described polyvinyl acetal foam materials and acyl chlorides is 2:5 ~ 20.
3. preparation method according to claim 1 is characterized in that, described acylation catalyst is pyridine, DMAP, diethylamine or triethylamine.
4. preparation method according to claim 3 is characterized in that, the mass ratio of described acylation catalyst and polyvinyl acetal foam materials is 0.2 ~ 0.8:2.
5. preparation method according to claim 1 is characterized in that, described dewatering agent is 4A level molecular sieve, silica gel, anhydrous magnesium sulfate, anhydrous calciumsulphate or anhydrous sodium sulphate.
6. preparation method according to claim 5 is characterized in that, the mass ratio of described dewatering agent and polyvinyl acetal foam materials is 8 ~ 15:2.
7. preparation method according to claim 1 is characterized in that, described organic solvent is one or more in dimethyl sulfoxide (DMSO), dimethyl formamide, acetonitrile and the N-Methyl pyrrolidone.
8. preparation method according to claim 1 is characterized in that, described organic solvent is one or more in toluene, dimethylbenzene, chlorobenzene and the tetracol phenixin.
9. according to claim 7 or 8 described preparation methods, it is characterized in that the mass ratio of the volume of described organic solvent and polyvinyl acetal foam materials is (80 ~ 150) mL:2g.
10. polymer-modified foam materials that is made by each described preparation method of claim 1 ~ 9.
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| CN104725662A (en) * | 2013-12-18 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Lipophilic polyurethane sponge and preparation method thereof |
| CN107513178A (en) * | 2017-08-31 | 2017-12-26 | 中国科学院长春应用化学研究所 | A kind of PVA-based foamed composite and preparation method thereof |
| CN109575353A (en) * | 2018-12-14 | 2019-04-05 | 中国科学院长春应用化学研究所 | A kind of Silanized hydrophobic modified polyvinylalcohol based porous materials and preparation method thereof |
| CN110565378A (en) * | 2019-09-16 | 2019-12-13 | 安徽大学 | Super-hydrophobic modified cotton fiber for oil-water separation and preparation method thereof |
| WO2022071089A1 (en) * | 2020-09-30 | 2022-04-07 | 積水化学工業株式会社 | Polyvinyl acetal resin |
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| CN103834131A (en) * | 2013-12-15 | 2014-06-04 | 浙江三赢医疗器械有限公司 | Super absorbent polyvinyl alcohol hydrogel, and preparation method and application thereof |
| CN104725662A (en) * | 2013-12-18 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Lipophilic polyurethane sponge and preparation method thereof |
| CN104725662B (en) * | 2013-12-18 | 2018-02-09 | 上海仪耐新材料科技有限公司 | A kind of lipophile polyurethane sponge and preparation method thereof |
| CN107513178A (en) * | 2017-08-31 | 2017-12-26 | 中国科学院长春应用化学研究所 | A kind of PVA-based foamed composite and preparation method thereof |
| CN107513178B (en) * | 2017-08-31 | 2020-12-08 | 中国科学院长春应用化学研究所 | Polyvinyl alcohol-based foam composite material and preparation method thereof |
| CN109575353A (en) * | 2018-12-14 | 2019-04-05 | 中国科学院长春应用化学研究所 | A kind of Silanized hydrophobic modified polyvinylalcohol based porous materials and preparation method thereof |
| CN109575353B (en) * | 2018-12-14 | 2020-12-08 | 中国科学院长春应用化学研究所 | Silanized hydrophobic modified polyvinyl alcohol-based porous material and preparation method thereof |
| CN110565378A (en) * | 2019-09-16 | 2019-12-13 | 安徽大学 | Super-hydrophobic modified cotton fiber for oil-water separation and preparation method thereof |
| CN110565378B (en) * | 2019-09-16 | 2022-04-05 | 安徽大学 | Super-hydrophobic modified cotton fiber for oil-water separation and preparation method thereof |
| WO2022071089A1 (en) * | 2020-09-30 | 2022-04-07 | 積水化学工業株式会社 | Polyvinyl acetal resin |
| JPWO2022071089A1 (en) * | 2020-09-30 | 2022-04-07 |
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