CN108822280A - A kind of preparation method of aqueous environment protection wet strengthening resin - Google Patents
A kind of preparation method of aqueous environment protection wet strengthening resin Download PDFInfo
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- CN108822280A CN108822280A CN201810578724.2A CN201810578724A CN108822280A CN 108822280 A CN108822280 A CN 108822280A CN 201810578724 A CN201810578724 A CN 201810578724A CN 108822280 A CN108822280 A CN 108822280A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/52—Epoxy resins
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
A kind of preparation method of aqueous environment protection wet strengthening resin, it is characterised in that：Epoxy resin E55 and 0.4~0.5 parts by weight polymerization inhibitor are added in the reaction kettle with blender and heating, cooling jacket, it is to slowly warm up to 70 DEG C, then acrylic acid and catalyst is added, then raises temperature to 90 ~ 100 DEG C, stops reaction when acid value is less than 5mg KOH/g；70 DEG C are reduced to, 45~55 parts by weight maleic anhydrides are then added, are warming up to 80~85 DEG C, when acid value is less than 5mg KOH/g, reaction stops, and is cooled to 40 DEG C~45 DEG C；Add dehydrated alcohol, is slow added into solid NaOH adjustment pH to 6~7；Continue under stirring, be slowly added to deionized water, obtains aqueous environment protection wet strengthening resin.
Description
Technical field
The present invention relates to a kind of preparation methods of aqueous environment protection wet strengthening resin.
Background technique
Wet strength refers to, in certain time, paper is put into the paper strength obtained after soaking in water.Plain paper is moistened
After wet, the 2%-10% or so of its original dry strength can only be kept.It is hygroscopic since paper pulp fiber has the hydrophily of height, when
When paper and water contact, under the action of water, the balanced structure of itself is destroyed, thus makes its wet strength drop more obvious than dry strength
It is low.For certain Paper or cardboards, because having higher requirement to wet strength, the intensity of plain paper itself is unable to satisfy demand, just
The additive of some enhancing paper wet strengths need to be added in paper pulp, the substance being added is wet strength agent.
The wet strength of usual paper is with the wet strength of paper（Intensity after dry paper rewetting）The ratio of dry strength is indicated, intensity
Property is often indicated with tensile strength.By add wet strength agent, produce retain 50% or more dry tensile strength wet-strength paper be can
Can.But the wet-strength paper of most of types can only retain the dry tensile strength of 20%-40% after with water saturates.It is some kinds of
Paper, such as toilet paper, if they without wet strength agent may some wet strengths all do not have, therefore, if this kind of paper is saturated
The dry tensile strength that 10%-20% can be retained afterwards, is also considered as wet-strength paper.
Common wet strength agent has polyethyleneimine（PEI）, Lauxite（UF）, polyamide epichlorohydrin resin（PAE）
Deng all having good wet potent fruit, while there is also some disadvantages, such as Lauxite（UF）And melamine resin
（MF）Though it is earliest using the time, since it contains free formaldehyde, environment is polluted, its application is limited, is prohibited in recent years by various countries
With；The wet potent fruit of PAE is good, and various countries are growing day by day to its demand, but it is expensive, and broken is not degradable, contains carcinogenic substance
The disadvantages of matter organochlorine；Dialdehyde starch（DAS）It is more early using the time, but have and cause the iodide of very big pollution to discharge environment,
Usage amount tends to reduce.
Nowadays, traditional wet strength agent has been unable to meet the needs of people, and in order to preferably improve papery, meet demand is various
Novel wet strength agent product category emerges one after another.In view of the requirement of environmental protection, and wet end chemistry factor is considered, such as the receiving of paper pulp
Property, pH value, solidification temperature, with intermiscibility, first-past retention, even distribution and the ability of anti-interference object of other auxiliary agents etc.,
Exploitation pollution-free high-efficient wet strength agent is imperative development trend from now on.
Existing novel environment friendly cross-linking system is mostly the cross-linking system with fiber-reactive type, utilizes the novel of these cross-linking systems
Wet strength agent is not commercialized yet, be because they also respectively have a disadvantage, it is such as at high cost, solidification temperature is too high, make paper embrittlement, contain admittedly it is low
Deng.Therefore, these novel environment friendly cross-linking systems also need to further investigate, and such as reduce cost to natural material transplanting, improve polymerization work
Skill increases molecular weight, the technique that exploitation can be practical, research repulping performance etc..
Polystyrene/glycidyl methacrylate wet strength agent can substitute existing wet strength agent, to meet society
Requirement to environmental protection, so the efficiency of wet strength agent is improved, reduce the cost of wet strength agent preparation.
Propylene oxide acid diester is 2 epoxy group open loop cyclic ester ring esterifications by acrylic acid and epoxy resin
Made from esterification obtained.There is the epoxy groups of three-membered ring in epoxy molecule structure, have very strong open loop energy
Power and special Cloud Distribution, reactivity are very high.The Cloud Distribution of epoxy group, which makes it not only, to be had electrophilicity but also has
Nucleophilicity, nucleopilic reagent are easy the C on attack ringδ+, electrophilic reagent is easy to attack oxygen atom, and two kinds of reagents can cause epoxy
The ring-opening reaction of base.In addition, since ternary cyclic linkage angle is 60oLeft and right, than normal bond angle 109oMuch smaller, tension is big, holds
Easy open loop, so, epoxy group has very high reactivity, it is with amino, carboxyl, hydroxyl, acid anhydrides etc. can be carried out and react.
Epoxy group is not reacted generally at normal temperature with carboxyl, needs to react in 100 DEG C or so heating, this reaction
It can be promoted to react by basic catalysts such as tertiary amine, quaternary amines.In acid condition, the nucleopilic reagents such as tertiary amine, quaternary ammonium salt are easy
Carbonium ion is attacked, ring-opening reaction occurs, reaction starts only carboxyl to the esterification of epoxy ring-opening, when carboxyl is by whole
After reaction, basic catalyst will make hydroxyl and epoxy group that etherification reaction occur.In the presence of basic catalyst, epoxy group with
The reaction of hydroxyl can carry out at a lower temperature.
Key reaction is that epoxy group is reacted with the esterification by ring opening of acrylic acid in synthetic reaction, but it may also happen that acrylic acid
Self-polymeric reaction and acrylic acid and epoxy resin in side reactions, the side reaction such as the esterification of hydroxyl will affect conjunction
At propylene oxide acid diester final performance, the failure of an experiment is even resulted in.
It can be seen from the above, in addition to there are the esterification by ring opening of epoxy group and acrylic acid in propylene oxide acid diester synthetic reaction
Reaction, there is also a variety of side reactions, and wherein the self-polymeric reaction of acrylic acid will lead to carbon-carbon double bond loss or even implode into macromolecule
Product, and the self-polymeric reaction of epoxy acrylate, epoxy group are reacted with etherification of hydroxyl groups, not only will affect reaction rate, Er Qiehui
Increase system viscosity, is finally unfavorable for reaction and carries out, therefore the control of raw material proportioning and reaction condition is particularly significant.
Epoxy resin is the primary raw material of synthesizing epoxy acrylate, different epoxy resin its molecular weight, epoxide number etc.
It is different, so different epoxy resin directly influences the content and its performance of propylene oxide acid diester double bond, while also can
The carboxyl-content of propylene oxide acid diester maleic anhydride addition compound is influenced, to further influence the water-soluble of final product
Property.Bisphenol-A type epoxy resin is source one of the most convenient, cheap epoxy resin.
Epoxide number is bigger, and the viscosity of epoxy resin is bigger, and also just meaning molecular weight is bigger, comes from the angle of traditional wet strength agent
It sees, molecular weight is bigger, and cross-linking effect is better, but the present invention is based on this principles of free radical polymerization, it is desirable to synthesizing epoxy third
It is The more the better that olefin(e) acid ester contains double bond amount, is just conducive to epoxy acrylate Raolical polymerizable in page, while rear
It is also required for considerable amount of hydroxyl in stage water-soluble modification, this requires more epoxy groups to react introducing foot with acrylic acid
Enough double bonds and hydroxyl.In addition, molecular weight is bigger, softening point is higher, and viscosity is too big, is unfavorable for homogeneous reaction.So the present invention selects
Raw material of the epoxy resin E-55 as synthesizing epoxy acrylate is selected.
Chinese patent CN201610758508.7 discloses a kind of preparation method of composite paper wet strength agent, and it is wet to belong to paper
Strong agent preparation technical field.The present invention will first activate ethanedioic acid by carbonyl dimidazoles, be made with 3-phoshoglyceric acid
For modifying agent, catalysis reaction is carried out by palladium-carbon catalyst, pre- modified polyamide mixed liquor is made, then by extracting discarded mushroom
Microorganism in mushroom culture medium generates free chloride ion in progress reaction process and is consumed, led to addition epoxychloropropane
The enzymic catalytic reaction of microorganism generation is crossed, so that composite paper wet strength agent be made.The beneficial effects of the invention are as follows：Present invention preparation
Step is simple, and the wet potent fruit of gained wet strength agent is good, high using rear paper strength；Utilize discarded mushroom culture medium and amino acid solution
Modified bacterium solution obtained carries out microorganism and is modified, and can effectively remove remaining organochlorine, gained wet strength agent content of organic chloride<
0.09%, solid content>50.6%.
Chinese patent CN201610452057.4 discloses the preparation method and wet strength agent of a kind of wet strength agent, this method packet
It includes：By the Polyamide-Polyamsne-Epichlorohydrin solution of 30-100 parts by weight, the polyvinyl alcohol of 40-80 parts by weight, 55-120 weight
Part paraben esters, the potassium titanate crystal whisker of 5-35 parts by weight, the linolenic acid of 10-30 parts by weight, 10-20 parts by weight propylene glycol,
It is carried out in homogenizer at 50-80 DEG C after the water-soluble cellulose of 2-15 parts by weight and the water mixing of 150-1000 parts by weight equal
Matter 1-5 hours, obtain wet strength agent.Wet strength agent of the invention can guarantee the intensity for guaranteeing paper while paper pliability.
Chinese patent CN201610451185.7 discloses the preparation method and wet strength agent of a kind of wet strength agent, this method packet
It includes：By the polyphenylene oxide of 30-100 parts by weight, the catalyst of 1-6 parts by weight, the ethyl alcohol of 5-35 parts by weight, 10-30 parts by weight meat
Myristate stearic acid, 3-10 parts by weight polyisocyanates, the organic solvent of 100-400 parts by weight, 10-80 parts by weight second two
In 100-200 DEG C of reflux after the epoxychloropropane mixing of amine, the diethylenetriamine of 20-150 parts by weight and 10-100 parts by weight
At a temperature of carry out back flow reaction 1-10 hours, after filtering, obtain wet strength agent.Wet strength agent of the invention can increase substantially paper
Wet strength and folding strength.
As wet strength agent for papermaking, not only wants that network structure can be cross-linked to form in page, protects hydrogen bond between fiber,
It needs wet strength agent that can be uniformly dispersed in slurry simultaneously, and there is certain charge, could effectively be adsorbed on fiber table
Face.But epoxy resin and the reaction product of acrylic acid itself do not have water solubility, without there is charge, so needing first to carry out it
Emulsification could use, and better method is to the water-soluble modification of the reaction product of epoxy resin and acrylic acid progress, we are with suitable
Anhydride maleique carries out water-soluble modification to it, and modified epoxy acrylate has preferable water solubility, and with a certain amount of
Charge more uniform can be attached on fiber.
Summary of the invention
To achieve the goals above, technology of the invention is realized in：A kind of system of aqueous environment protection wet strengthening resin
Preparation Method, it is characterised in that：100~105 parts by weight epoxy are added in the reaction kettle with blender and heating, cooling jacket
Resin E55 and 0.4~0.5 parts by weight polymerization inhibitor, are sufficiently stirred, are to slowly warm up to 70 DEG C, and 38~42 weight of acrylic acid is then added
The catalyst for measuring part and 0.8~1.2 parts by weight, then raises temperature to 90 ~ 100 DEG C, is kept the temperature, and per half an hour surveys a hypo acid
Value stops reaction when acid value is less than 5mg KOH/g；Be reduced to 70 DEG C, add 0.4~0.5 parts by weight polymerization inhibitor, 0.8~
The catalyst of 1.2 parts by weight is sufficiently stirred, and 50~60 parts by weight maleic anhydrides are then added, are warming up to 80~85 DEG C, into
Row heat preservation surveys an acid value every half an hour, and when acid value is less than 5mg KOH/g, reaction stops, and is cooled to 40 DEG C~45
℃；Add 20~30 parts by weight dehydrated alcohols, continue to stir, is slow added into solid NaOH adjustment pH to 6~7；Continue to stir
Under, 200~250 parts by weight of deionized water are slowly added to, aqueous environment protection wet strengthening resin is obtained；
The catalyst is N, N- dimethylethanolamine；
The polymerization inhibitor is hydroquinone.
Embodiment：
Embodiment 1
100kg epoxy resin E55 and 0.4kg hydroquinone are added in the reaction kettle with blender and heating, cooling jacket,
It is sufficiently stirred, is to slowly warm up to 70 DEG C, the N of acrylic acid 38kg and 0.8kg is then added, N- dimethylethanolamine then heats up
It to 90 DEG C, is kept the temperature, per half an hour surveys an acid value, stops reaction when acid value is less than 5mg KOH/g；It is reduced to 70
DEG C, the N of 0.4kg hydroquinone, 0.8kg are added, N- dimethylethanolamine is sufficiently stirred, and 50kg maleic acid is then added
Acid anhydride is warming up to 80 DEG C, is kept the temperature, and surveys an acid value every half an hour, and when acid value is less than 5mg KOH/g, reaction stops,
It is cooled to 40 DEG C；Add 20kg dehydrated alcohol, continue to stir, is slow added into solid NaOH adjustment pH to 6；Continue under stirring,
It is slowly added to 200kg deionized water, obtains aqueous environment protection wet strengthening resin.
Embodiment 2
105kg epoxy resin E55 and 0.5kg hydroquinone are added in the reaction kettle with blender and heating, cooling jacket,
It is sufficiently stirred, is to slowly warm up to 70 DEG C, the N of acrylic acid 42kg and 1.2kg is then added, N- dimethylethanolamine then heats up
It to 100 DEG C, is kept the temperature, per half an hour surveys an acid value, stops reaction when acid value is less than 5mg KOH/g；It is reduced to
70 DEG C, the N of 0.5kg hydroquinone, 1.2kg are added, N- dimethylethanolamine is sufficiently stirred, and 60kg maleic two is then added
Acid anhydrides is warming up to 85 DEG C, is kept the temperature, and surveys an acid value every half an hour, and when acid value is less than 5mg KOH/g, reaction stops
Only, 45 DEG C are cooled to；Add 30kg dehydrated alcohol, continue to stir, is slow added into solid NaOH adjustment pH to 7；Continue to stir
Under, it is slowly added to 250kg deionized water, obtains aqueous environment protection wet strengthening resin.
Embodiment 3
100kg epoxy resin E55 and 0.5kg hydroquinone are added in the reaction kettle with blender and heating, cooling jacket,
It is sufficiently stirred, is to slowly warm up to 70 DEG C, the N of acrylic acid 42kg and 0.8kg is then added, N- dimethylethanolamine then heats up
It to 100 DEG C, is kept the temperature, per half an hour surveys an acid value, stops reaction when acid value is less than 5mg KOH/g；It is reduced to
70 DEG C, the N of 0.4kg hydroquinone, 1.2kg are added, N- dimethylethanolamine is sufficiently stirred, and 50kg maleic two is then added
Acid anhydrides is warming up to 85 DEG C, is kept the temperature, and surveys an acid value every half an hour, and when acid value is less than 5mg KOH/g, reaction stops
Only, 40 DEG C are cooled to；Add 30kg dehydrated alcohol, continue to stir, is slow added into solid NaOH adjustment pH to 6；Continue to stir
Under, it is slowly added to 250kg deionized water, obtains aqueous environment protection wet strengthening resin.
Embodiment 4
105kg epoxy resin E55 and 0.4kg hydroquinone are added in the reaction kettle with blender and heating, cooling jacket,
It is sufficiently stirred, is to slowly warm up to 70 DEG C, the N of acrylic acid 40kg and 1.2kg is then added, N- dimethylethanolamine then heats up
It to 90 DEG C, is kept the temperature, per half an hour surveys an acid value, stops reaction when acid value is less than 5mg KOH/g；It is reduced to 70
DEG C, the N of 0.5kg hydroquinone, 0.8kg are added, N- dimethylethanolamine is sufficiently stirred, and 55kg maleic acid is then added
Acid anhydride is warming up to 80 DEG C, is kept the temperature, and surveys an acid value every half an hour, and when acid value is less than 5mg KOH/g, reaction stops,
It is cooled to 45 DEG C；Add 20kg dehydrated alcohol, continue to stir, is slow added into solid NaOH adjustment pH to 7；Continue under stirring,
It is slowly added to 200kg deionized water, obtains aqueous environment protection wet strengthening resin.
Embodiment 5
102kg epoxy resin E55 and 0.45kg is added in the reaction kettle with blender and heating, cooling jacket to benzene two
Phenol is sufficiently stirred, and is to slowly warm up to 70 DEG C, then the N of addition acrylic acid 41kg and 1.0kg, N- dimethylethanolamine, then
95 DEG C are warming up to, is kept the temperature, per half an hour surveys an acid value, stops reaction when acid value is less than 5mg KOH/g；It reduces
To 70 DEG C, the N of 0.47kg hydroquinone, 1.1kg are added, N- dimethylethanolamine is sufficiently stirred, and 58kg is then added along fourth
Enedioic acid acid anhydride is warming up to 83 DEG C, is kept the temperature, every half an hour survey an acid value, when acid value be less than 5mg KOH/g, instead
It should stop, being cooled to 43 DEG C；Add 25kg dehydrated alcohol, continue to stir, is slow added into solid NaOH adjustment pH to 7；Continue
Under stirring, it is slowly added to 235kg deionized water, obtains aqueous environment protection wet strengthening resin.
Claims (1)
1. a kind of preparation method of aqueous environment protection wet strengthening resin, it is characterised in that：Having blender and heating, cooling jacket
Reaction kettle in 100~105 parts by weight epoxy resin E55 and 0.4~0.5 parts by weight polymerization inhibitor is added, be sufficiently stirred, slowly rise
Then the catalyst of acrylic acid 38~42 parts by weight and 0.8~1.2 parts by weight is added to 70 DEG C in temperature, then raise temperature to 90 ~
It 100 DEG C, is kept the temperature, per half an hour surveys an acid value, stops reaction when acid value is less than 5mg KOH/g；It is reduced to 70
DEG C, it adds 0.4~0.5 parts by weight polymerization inhibitor, the catalyst of 0.8~1.2 parts by weight is sufficiently stirred, 50~60 weights is then added
Part maleic anhydride is measured, 80~85 DEG C is warming up to, is kept the temperature, an acid value is surveyed every half an hour, when acid value is less than
5mg KOH/g, reaction stop, and are cooled to 40 DEG C~45 DEG C；Add 20~30 parts by weight dehydrated alcohols, continue to stir, then slowly adds
Enter solid NaOH adjustment pH to 6~7；Continue under stirring, be slowly added to 200~250 parts by weight of deionized water, obtains aqueous ring
Guarantor's type wet strengthening resin；
The catalyst is N, N- dimethylethanolamine；
The polymerization inhibitor is hydroquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810578724.2A CN108822280A (en) | 2018-06-07 | 2018-06-07 | A kind of preparation method of aqueous environment protection wet strengthening resin |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810578724.2A CN108822280A (en) | 2018-06-07 | 2018-06-07 | A kind of preparation method of aqueous environment protection wet strengthening resin |
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| CN108822280A true CN108822280A (en) | 2018-11-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575278A (en) * | 2018-11-22 | 2019-04-05 | 山东同创精细化工股份有限公司 | A kind of strong PAE of high humidity and preparation method thereof |
-
2018
- 2018-06-07 CN CN201810578724.2A patent/CN108822280A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575278A (en) * | 2018-11-22 | 2019-04-05 | 山东同创精细化工股份有限公司 | A kind of strong PAE of high humidity and preparation method thereof |
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