CN106832674A - A kind of environment-friendly type interior decoration film of removable formaldehyde and preparation method thereof - Google Patents
A kind of environment-friendly type interior decoration film of removable formaldehyde and preparation method thereof Download PDFInfo
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- CN106832674A CN106832674A CN201710107341.2A CN201710107341A CN106832674A CN 106832674 A CN106832674 A CN 106832674A CN 201710107341 A CN201710107341 A CN 201710107341A CN 106832674 A CN106832674 A CN 106832674A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The invention discloses a kind of environment-friendly type interior decoration film of removable formaldehyde, it is made up of the raw material of following weight portion：100 parts of polyvinyl chloride resin powder, 3 10 parts of diethanol amine, 32 58 parts of methyl alcohol, 7 19 parts of methyl acrylate, 18 32 parts of montmorillonite, 21 33 parts of trimethylolpropane, 14 parts of p-methyl benzenesulfonic acid, 28 42 parts of diethyl malonate, 25 parts of Anhydrous potassium carbonate, TiCl4 13 24 parts, appropriate hydrochloric acid solution distills appropriate amount of water, appropriate absolute ethyl alcohol, 43 58 parts of DOTP plasticizer.The present invention utilizes the layer structure of montmorillonite, realize the stable curing to titanium deoxide catalyst, hyperbranched polyurethane intercalation modifying montmorillonite is utilized afterwards, the physical absorption of formaldehyde and chemical reaction are combined, accomplish to eliminate the purpose of formaldehyde in absorption, compound is added in decorating film base-material afterwards, it is possessed the formaldehyde elimination function that conventional decorative film does not possess.
Description
Technical field
The present invention relates to a kind of formaldehyde scavenger, and in particular to a kind of environment-friendly type interior decoration film of removable formaldehyde and its
Preparation method.
Background technology
Formaldehyde is a kind of extremely strong bactericide, is widely used in industrial production.Formaldehyde is manufacture synthetic resin, paint, modeling
The raw material of material and staple fibre, is the weight of wood-based panel industry manufacture urea-formaldehyde resin adhesive, melamine resin adehsive and phenolic resin glue
Want raw material.Formaldehyde is more highly toxic material, and formaldehyde is in second on China's toxic chemical priority acccess control list.Formaldehyde
It is defined as carcinogenic by the World Health Organization and causes deformed material, be generally acknowledged allergen, is also prominent potential strong cause
Become one of thing.
At present, the main method that people eliminate formaldehyde in indoor air pollution is to use formaldehyde eliminating agent.But existing market
The common formaldehyde eliminating agent product of upper sale formaldehyde elimination amount within a certain period of time is limited and persistence of effect is poor, leads to
The term of validity of normal these formaldehyde eliminating agents only has several days time.
Wang Xuechuan, Yuan Xuzheng et al. are at it《The synthesis and application of active methylene group class dissaving polymer methanal trapping agent》
It is that raw material is obtained AB by Michael addition reactions with diethanol amine (DEA) and methyl acrylate (MA) in one text2Type monomer,
Under Catalyzed by p-Toluenesulfonic Acid, there is ester exchange reaction with trimethylolpropane, be obtained a kind of superbrnaching end-hydroxy it is poly- (amine-
Ester), afterwards and diethyl malonate, terminal groups modification is carried out to terminal hydroxy group hyperbranched poly (amine -ester) by ester exchange reaction, so that
Active methylene group class dissaving polymer (HPAM) is prepared, formaldehyde can be effectively caught, but its acquisition procedure is slower.
Montmorillonite (MMT) is the two-dimensional layer silicate mineral that a class interlayer has exchangeable cations, with good swollen
Swollen property, adsorptivity and cation exchange property, favourable bar is provided for many intercalated materials carry out the compound insertion reaction of interlayer
Part.Therefore can be realized using montmorillonite it is immobilized to stablizing for catalyst, while can be used to formaldehyde adsorption, to reach purify air
Purpose.
The content of the invention
The present invention is in view of the shortcomings of the prior art, there is provided a kind of environment-friendly type interior decoration film of removable formaldehyde and its preparation
Method.
A kind of environment-friendly type interior decoration film of removable formaldehyde, is made up of the raw material of following weight portion：Corvic
100 parts of powder, diethanol amine 3-10 parts, methyl alcohol 32-58 parts, methyl acrylate 7-19 parts, montmorillonite 18-32 parts, trihydroxy methyl third
Alkane 21-33 parts, p-methyl benzenesulfonic acid 1-4 parts, diethyl malonate 28-42 parts, Anhydrous potassium carbonate 2-5 parts, TiCl4 13-24 parts, salt
Appropriate acid solution, distills appropriate amount of water, appropriate absolute ethyl alcohol, 43-58 parts of DOTP plasticizer.
Comprise the following steps that：
（1）Prepare TiCl4Pillaring agent：
By TiCl4It is added in hydrochloric acid solution, with distilled water diluting to Ti4+0.8mol/L and 0.2- are respectively with HCl concentration
0.4mol/L, obtains final product TiCl4Pillaring agent；
（2）Montmorillonite is dispersed in distilled water, above-mentioned TiCl is slowly added dropwise4Pillaring agent, stirring reaction 4-5 hours, adjusts pH value
To 2-3, stirring reaction 3-5 hours, centrifugation afterwards with absolute ethanol washing, suction filtration, was washed, dried, at 500 DEG C afterwards
Lower calcination product 45-70 minutes, through cooling, grinding, obtains final product Titania Pillared Montmorillonites；
（3）The synthesis of reaction monomers：
Add diethanol amine and methyl alcohol, mixture to be stirred at room temperature to diethanol amine after being completely dissolved in there-necked flask, delay
Slow that methyl acrylate is added dropwise, charging is warming up to 30-40 DEG C insulation reaction 3-5 hours, then vacuumizes removing methyl alcohol, obtains after finishing
To grease；
（4）The preparation of superbrnaching end-hydroxy Polyurethane modified montmorillonoid：
Step is added in there-necked flask（2）Titania Pillared Montmorillonites, trimethylolpropane and p-methyl benzenesulfonic acid, stirring are mixed
Compound 10-25 minutes, 110-120 DEG C is warming up to, starts to stir and be added dropwise step（3）Reaction monomers, 110-130 DEG C of reaction 30-
After 50 minutes, continuation is reacted in being transferred to Rotary Evaporators, untill system is bloated there is no bubble, obtains terminal hydroxy group over-expense
Change Polyurethane modified montmorillonoid；
（5）Diethyl malonate and catalyst Anhydrous potassium carbonate are added in there-necked flask, after stirring, is to slowly warm up to
95-105 DEG C, start to be slowly added to step（4）Product, charging is finished latter insulation reaction 4-5 hours, then vacuum distillation, takes out true
Vacancy is managed, and obtains ternary complex；
（6）By step（5）Compound mixes with polyvinyl chloride resin powder, DOTP plasticizer, and control temperature turns at 115-135 DEG C
Speed under the conditions of 600-700r/min stir 5-8 minute, then be cooled to 60-80 DEG C continue stirring 3-5 minutes, material is formed
One dispersion；
（7）Above-mentioned dispersion is delivered in banbury, is kneaded 6-10 minutes at 175-190 DEG C, begun to pratise at 195-205 DEG C afterwards
5-10 minutes, extrusion filtering was obtained final product through four-roll calendaring, traction, embossing, cooling and shaping, trimming, coiling technique.
Wherein, the concentration of described hydrochloric acid solution is 2.0mol/L.
Wherein, step（1）Prepare TiCl4During pillaring agent, Ti:HCl mol ratios are 2:1.
Wherein, step（2）Middle drying condition is drying temperature at 65-73 DEG C, drying time 3-6 hours.
Compared with prior art, the present invention has advantages below：
（1）The present invention is prepared for superbrnaching end-hydroxy Polyurethane intercalation modifying montmorillonite, reacts right with diethyl malonate afterwards
Polymer carries out blocking modification, and hyperbranched polyurethane is a three-dimensional molecular structure for nearly ball-type, exists in the inside of molecule empty
Chamber, PARA FORMALDEHYDE PRILLS(91,95) small molecule has certain suction-operated, while using the absorption property of montmorillonite, by formaldehyde fast Acquisition, absorption
On remover, in addition because its a large amount of active methylene group functional group contained can react with formaldehyde, first can be effectively reduced
The content of aldehyde.
（2）The present invention realizes the stable curing to titanium deoxide catalyst using the layer structure of montmorillonite, improves to first
The photocatalytic degradation efficiency of aldehyde, the physical absorption of formaldehyde and chemical reaction are combined, and finally change into formaldehyde nontoxic, tasteless
Material, accomplishes to eliminate the purpose of formaldehyde in absorption, the effect of quick, lasting purify air is reached, to sky when actually used
Other poisonous odor gas in gas also have stronger suction-operated, and practical effect is good.
（3）Be added to Titanium dioxide/montmorillonite/hyperbranched polyurethane ternary complex in decorating film base-material by the present invention,
It is possessed the formaldehyde elimination function that conventional decorative film does not possess, have functions that to remove Formaldehyde Pollution of Indoor Air.
Specific embodiment
A kind of environment-friendly type interior decoration film of removable formaldehyde, is made up of the raw material of following weight portion：Corvic
100 parts of powder, 5 parts of diethanol amine, 40 parts of methyl alcohol, 13 parts of methyl acrylate, 23 parts of montmorillonite, 26 parts of trimethylolpropane, to first
3 parts of benzene sulfonic acid, 34 parts of diethyl malonate, 4 parts of Anhydrous potassium carbonate, TiCl4 19 parts, appropriate hydrochloric acid solution distills appropriate amount of water, nothing
Appropriate water-ethanol, 47 parts of DOTP plasticizer.
Comprise the following steps that：
（1）Prepare TiCl4Pillaring agent：
By TiCl4It is added in hydrochloric acid solution, with distilled water diluting to Ti4+0.8mol/L and 0.3mol/ are respectively with HCl concentration
L, obtains final product TiCl4Pillaring agent；
（2）Montmorillonite is dispersed in distilled water, above-mentioned TiCl is slowly added dropwise4Pillaring agent, stirring reaction 4 hours adjusts pH value extremely
2.5, stirring reaction 4 hours, afterwards centrifugation with absolute ethanol washing, suction filtration, is washed, dried afterwards, is forged at 500 DEG C
Burn product 60 minutes, through cooling, grinding, obtain final product Titania Pillared Montmorillonites；
（3）The synthesis of reaction monomers：
Add diethanol amine and methyl alcohol, mixture to be stirred at room temperature to diethanol amine after being completely dissolved in there-necked flask, delay
Slow to be added dropwise methyl acrylate, charging is warming up to 35 DEG C of insulation reactions 4 hours after finishing, then vacuumize removing methyl alcohol, obtains oil
Shape thing；
（4）The preparation of superbrnaching end-hydroxy Polyurethane modified montmorillonoid：
Step is added in there-necked flask（2）Titania Pillared Montmorillonites, trimethylolpropane and p-methyl benzenesulfonic acid, stirring are mixed
Compound 20 minutes, is warming up to 115 DEG C, starts to stir and be added dropwise step（3）Reaction monomers, after 120 DEG C are reacted 40 minutes, are transferred to
Continue to react in Rotary Evaporators, untill system is bloated there is no bubble, obtain the ester modified illiteracy of superbrnaching end-hydroxy polyamine
De- soil；
（5）Diethyl malonate and catalyst Anhydrous potassium carbonate are added in there-necked flask, after stirring, is to slowly warm up to
100 DEG C, start to be slowly added to step（4）Product, charging finishes rear insulation reaction 4 hours, and then vacuum distillation vacuumizes place
Reason, obtains ternary complex；
（6）By step（5）Compound mixes with polyvinyl chloride resin powder, DOTP plasticizer, and at 125 DEG C, rotating speed exists control temperature
Stirred 6 minutes under the conditions of 650r/min, then be cooled to 70 DEG C and continue to stir 4 minutes, material is formed homogeneous dispersion；
（7）Above-mentioned dispersion is delivered in banbury, is kneaded 8 minutes at 180 DEG C, begun to pratise 6 minutes at 200 DEG C afterwards, extruded
Filtering, obtains final product through four-roll calendaring, traction, embossing, cooling and shaping, trimming, coiling technique.
Wherein, the concentration of described hydrochloric acid solution is 2.0mol/L.
Wherein, step（1）Prepare TiCl4During pillaring agent, Ti:HCl mol ratios are 2:1.
Wherein, step（2）Middle drying condition is drying temperature at 65-73 DEG C, drying time 3-6 hours.
Claims (5)
1. the environment-friendly type interior decoration film of a kind of removable formaldehyde, it is characterised in that be made up of the raw material of following weight portion：Polychlorostyrene
100 parts of vinyl powder, diethanol amine 3-10 parts, methyl alcohol 32-58 parts, methyl acrylate 7-19 parts, montmorillonite 18-32 parts, three
Hydroxymethyl-propane 21-33 parts, p-methyl benzenesulfonic acid 1-4 parts, diethyl malonate 28-42 parts, Anhydrous potassium carbonate 2-5 parts, TiCl4
13-24 parts, appropriate hydrochloric acid solution distills appropriate amount of water, appropriate absolute ethyl alcohol, 43-58 parts of DOTP plasticizer.
2. the preparation method of the environment-friendly type interior decoration film of a kind of removable formaldehyde according to claims 1, its feature
It is to comprise the following steps that：
（1）Prepare TiCl4Pillaring agent：
By TiCl4It is added in hydrochloric acid solution, with distilled water diluting to Ti4+0.8mol/L and 0.2- are respectively with HCl concentration
0.4mol/L, obtains final product TiCl4Pillaring agent；
（2）Montmorillonite is dispersed in distilled water, above-mentioned TiCl is slowly added dropwise4Pillaring agent, stirring reaction 4-5 hours, adjusts pH value extremely
2-3, stirring reaction 3-5 hours, centrifugation afterwards with absolute ethanol washing, suction filtration, was washed, dried, at 500 DEG C afterwards
Calcination product 45-70 minutes, through cooling, grinding, obtain final product Titania Pillared Montmorillonites；
（3）The synthesis of reaction monomers：
Add diethanol amine and methyl alcohol, mixture to be stirred at room temperature to diethanol amine after being completely dissolved in there-necked flask, delay
Slow that methyl acrylate is added dropwise, charging is warming up to 30-40 DEG C insulation reaction 3-5 hours, then vacuumizes removing methyl alcohol, obtains after finishing
To grease；
（4）The preparation of superbrnaching end-hydroxy Polyurethane modified montmorillonoid：
Step is added in there-necked flask（2）Titania Pillared Montmorillonites, trimethylolpropane and p-methyl benzenesulfonic acid, stirring are mixed
Compound 10-25 minutes, 110-120 DEG C is warming up to, starts to stir and be added dropwise step（3）Reaction monomers, 110-130 DEG C of reaction 30-
After 50 minutes, continuation is reacted in being transferred to Rotary Evaporators, untill system is bloated there is no bubble, obtains terminal hydroxy group over-expense
Change Polyurethane modified montmorillonoid；
（5）Diethyl malonate and catalyst Anhydrous potassium carbonate are added in there-necked flask, after stirring, is to slowly warm up to
95-105 DEG C, start to be slowly added to step（4）Product, charging is finished latter insulation reaction 4-5 hours, then vacuum distillation, takes out true
Vacancy is managed, and obtains ternary complex；
（6）By step（5）Compound mixes with polyvinyl chloride resin powder, DOTP plasticizer, and control temperature turns at 115-135 DEG C
Speed under the conditions of 600-700r/min stir 5-8 minute, then be cooled to 60-80 DEG C continue stirring 3-5 minutes, material is formed
One dispersion；
（7）Above-mentioned dispersion is delivered in banbury, is kneaded 6-10 minutes at 175-190 DEG C, begun to pratise at 195-205 DEG C afterwards
5-10 minutes, extrusion filtering was obtained final product through four-roll calendaring, traction, embossing, cooling and shaping, trimming, coiling technique.
3. the preparation method of the environment-friendly type interior decoration film of a kind of removable formaldehyde according to claims 1,2, it is special
Levy and be, the concentration of described hydrochloric acid solution is 2.0mol/L.
4. the preparation method of the environment-friendly type interior decoration film of a kind of removable formaldehyde according to claims 2, its feature
It is, step（1）Prepare TiCl4During pillaring agent, Ti:HCl mol ratios are 2:1.
5. the preparation method of the environment-friendly type interior decoration film of a kind of removable formaldehyde according to claims 2, its feature
It is, step（2）Middle drying condition is drying temperature at 65-73 DEG C, drying time 3-6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710107341.2A CN106832674A (en) | 2017-02-27 | 2017-02-27 | A kind of environment-friendly type interior decoration film of removable formaldehyde and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710107341.2A CN106832674A (en) | 2017-02-27 | 2017-02-27 | A kind of environment-friendly type interior decoration film of removable formaldehyde and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628033A (en) * | 2018-12-29 | 2019-04-16 | 广西六万山林业有限公司 | A kind of environmental protection type veneer board adhesive and the preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754252A (en) * | 2016-03-04 | 2016-07-13 | 广东尚鑫新材料股份有限公司 | High-definition transparent household purifying film and preparation method thereof |
| CN105968633A (en) * | 2016-05-26 | 2016-09-28 | 浙江明士达新材料有限公司 | Formaldehyde-removal indoor decorative film |
-
2017
- 2017-02-27 CN CN201710107341.2A patent/CN106832674A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754252A (en) * | 2016-03-04 | 2016-07-13 | 广东尚鑫新材料股份有限公司 | High-definition transparent household purifying film and preparation method thereof |
| CN105968633A (en) * | 2016-05-26 | 2016-09-28 | 浙江明士达新材料有限公司 | Formaldehyde-removal indoor decorative film |
Non-Patent Citations (3)
| Title |
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| 张人佶主编: "《先进成形制造实用技术》", 31 August 2009, 北京：清华大学出版社 * |
| 王学川等: "活泼亚甲基类超支化聚合物甲醛捕获剂的合成及应用", 《中国皮革》 * |
| 董梦琴: "纳米二氧化钛/蒙脱土复合材料的制备及其催化活性研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628033A (en) * | 2018-12-29 | 2019-04-16 | 广西六万山林业有限公司 | A kind of environmental protection type veneer board adhesive and the preparation method and application thereof |
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