CN110655731A - Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde - Google Patents

Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde Download PDF

Info

Publication number
CN110655731A
CN110655731A CN201810706315.6A CN201810706315A CN110655731A CN 110655731 A CN110655731 A CN 110655731A CN 201810706315 A CN201810706315 A CN 201810706315A CN 110655731 A CN110655731 A CN 110655731A
Authority
CN
China
Prior art keywords
removing formaldehyde
formula
polyvinyl chloride
compound represented
article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810706315.6A
Other languages
Chinese (zh)
Other versions
CN110655731B (en
Inventor
霍鑫
王卫峰
陈敬浩
史志宇
李梦玲
向亮
余鹏
贺鹏
江勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Priority to CN201810706315.6A priority Critical patent/CN110655731B/en
Priority to PCT/IB2019/055477 priority patent/WO2020003215A1/en
Priority to TW108123127A priority patent/TW202010787A/en
Publication of CN110655731A publication Critical patent/CN110655731A/en
Application granted granted Critical
Publication of CN110655731B publication Critical patent/CN110655731B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
    • B60N3/00—Arrangements or adaptations of other passenger fittings, not otherwise provided for
    • B60N3/04—Arrangements or adaptations of other passenger fittings, not otherwise provided for of floor mats or carpets
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G27/00—Floor fabrics; Fastenings therefor
    • A47G27/02—Carpets; Stair runners; Bedside rugs; Foot mats
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Transportation (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a polyvinyl chloride composition for removing formaldehyde and an article for removing formaldehyde. Specifically, the present invention provides a polyvinyl chloride composition for removing formaldehyde, comprising, based on 100 parts by weight of the total weight of the composition: 30-60% by weight of a polyvinyl chloride resin; 25-50 wt% of a plasticizer; 3-25 wt% of a filler; 0.01-5 wt% of an organic acid; 0.01-5 wt% of an alkylamine alcohol; 0.02-10 wt% of an organic solvent; and 0.03-15 wt% of water. The article for removing formaldehyde manufactured from the polyvinyl chloride composition for removing formaldehyde according to the present invention has excellent formaldehyde removing effect and good odor grade.

Description

Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde
Technical Field
The present invention relates to the field of pollution control in a room or a vehicle, and in particular, to a polyvinyl chloride (PVC) composition for removing formaldehyde and a foot mat manufactured therefrom.
Background
Harmful gases such as formaldehyde are one of the main pollution sources in newly-installed and repaired houses. Various products for eliminating harmful gases such as formaldehyde have been developed to absorb or adsorb indoor harmful gas pollution.
In addition, the automobile foot pad is a common article in an automobile, can absorb water, absorb dust and remove dirt, effectively prevents residual moisture, dirt and the like on the sole from causing sliding with the clutch, the brake and the accelerator, avoids potential safety hazards and reduces the possibility of polluting and damaging the interior trim. But in many new cars, can remain a lot of organic gas, for example formaldehyde and all kinds of VOC gas, car callus on the sole if can provide formaldehyde removal effect, will solve the puzzlement of many people. Especially, the foot pad of the automobile has large using area in the automobile and is beneficial to removing formaldehyde.
However, very few footbeds with similar functions are currently available on the market. At present, products for removing formaldehyde statically in a vehicle are divided into two types, one type is a spray type spray, and the other type is an activated carbon bag. Some of the spray products contain titanium dioxide nanoparticles, which can react quickly with formaldehyde, but because formaldehyde is constantly volatilized, the spray sprays fail quickly. The activated carbon bag type products are mostly made of common coconut shell activated carbon, formaldehyde is absorbed only by adsorption, and after the adsorption is saturated, the activated carbon bag type products are easy to desorb, so that the concentration of the formaldehyde is increased again.
Therefore, there is a need to develop a product for pollution control in a room or a vehicle, which has no organic gas odor and can statically adsorb formaldehyde for a long period of time.
Disclosure of Invention
Starting from the technical problems set forth above, it is an object of the present invention to provide a polyvinyl chloride composition for removing formaldehyde and an article for removing formaldehyde, which are manufactured from the polyvinyl chloride composition for removing formaldehyde according to the present invention, and have excellent formaldehyde removal effects and good odor grade.
The present inventors have made intensive studies and completed the present invention.
According to an aspect of the present invention, there is provided a polyvinyl chloride composition for removing formaldehyde, comprising, based on 100 parts by weight of the total weight of the composition:
30-60% by weight of a polyvinyl chloride resin;
25-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-5 wt% of an organic acid;
0.01-5 wt% of an alkylamine alcohol;
0.02-10 wt% of an organic solvent; and
0.03-15% by weight of water.
Optionally, the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure BDA0001713998950000021
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
Optionally, the alkylamine alcohol is a mixture of a compound represented by formula (1) and a compound represented by formula (2).
Optionally, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1: 4 to 4: 1.
Optionally, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1: 2 to 2: 1.
Optionally, the alkylamine alcohol is selected from one or more of tromethamine, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol.
Optionally, the alkylamine alcohol is present in an amount of 0.1 to 5 wt%, based on 100 wt% of the total weight of the polyvinyl chloride composition for removing formaldehyde.
Optionally, the alkylamine alcohol is present in an amount of 0.5 to 1 wt%, based on 100 wt% of the total weight of the polyvinyl chloride composition for removing formaldehyde.
Optionally, the organic acid is C8-C18An organic acid.
Optionally, said C8-C18The organic acid is at least one of caprylic acid and isostearic acid.
Optionally, the polyvinyl chloride resin has a weight average molecular weight of 1000g/mol to 2000 g/mol.
Optionally, the polyvinyl chloride resin is polyvinyl chloride resin powder.
Optionally, the plasticizer is an ester plasticizer.
Optionally, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate or a mixture thereof.
Optionally, the filler is calcium carbonate.
Optionally, the polyvinyl chloride composition for removing formaldehyde further comprises a solvent.
Optionally, the solvent is an N-alkyl pyrrolidone, wherein the number of carbon atoms in the alkyl group is from 1 to 8.
Optionally, the solvent is an alcohol having 1 to 3 carbon atoms.
According to another aspect of the present invention, there is provided an article for removing formaldehyde, comprising, based on 100 parts by weight of the total weight of the article:
40-60% by weight of a polyvinyl chloride resin;
30-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-6.67 wt% of an organic acid; and
0.01-6.67 wt% of alkylamine alcohol.
Optionally, the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure BDA0001713998950000031
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
Optionally, the alkylamine alcohol is a mixture of a compound represented by formula (1) and a compound represented by formula (2).
Optionally, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1: 4 to 4: 1.
Optionally, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1: 2 to 2: 1.
Optionally, the alkylamine alcohol is selected from one or more of tromethamine, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol.
Optionally, the alkylamine alcohol is present in an amount of from 0.1 to 6.67 wt%, based on 100 wt% of the total weight of the article for removing formaldehyde.
Optionally, the alkylamine alcohol is present in an amount of from 0.52 to 1.05 wt%, based on 100 wt% of the total weight of the article for removing formaldehyde.
Optionally, the organic acid is C8-C18An organic acid.
Optionally, said C8-C18The organic acid is at least one of caprylic acid and isostearic acid.
Optionally, the polyvinyl chloride resin has a weight average molecular weight of 1000g/mol to 2000 g/mol.
Optionally, the polyvinyl chloride resin is polyvinyl chloride resin powder.
Optionally, the plasticizer is an ester plasticizer.
Optionally, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate or a mixture thereof.
Optionally, the filler is calcium carbonate.
Optionally, the article for removing formaldehyde is a foot mat.
According to still another aspect of the present invention, there is provided an article for removing formaldehyde, the article for removing formaldehyde including a main body portion and a coating layer covering the main body portion, the coating layer comprising, based on 100 parts by weight in total:
40-60% by weight of a polyvinyl chloride resin;
30-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-6.67 wt% of an organic acid; and
0.01-6.67 wt% of alkylamine alcohol.
Optionally, the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure BDA0001713998950000051
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
Optionally, the alkylamine alcohol is a mixture of a compound represented by formula (1) and a compound represented by formula (2).
Optionally, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1: 4 to 4: 1.
Optionally, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1: 2 to 2: 1.
Optionally, the alkylamine alcohol is selected from one or more of tromethamine, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol.
Optionally, the alkylamine alcohol is present in an amount of 0.1 to 6.67 wt%, based on 100 wt% of the total weight of the coating.
Optionally, the alkylamine alcohol is present in an amount of 0.52 to 1.05 wt%, based on 100 wt% of the total weight of the coating.
Optionally, the organic acid is C8-C18An organic acid.
Optionally, said C8-C18The organic acid is at least one of caprylic acid and isostearic acid.
Optionally, the polyvinyl chloride resin has a weight average molecular weight of 1000g/mol to 2000 g/mol.
Optionally, the polyvinyl chloride resin is polyvinyl chloride resin powder.
Optionally, the plasticizer is an ester plasticizer.
Optionally, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate or a mixture thereof.
Optionally, the filler is calcium carbonate.
Optionally, the article for removing formaldehyde is a foot mat.
Compared with the prior art in the field, the invention has the advantages that:
1. the product for removing formaldehyde, which is manufactured by the polyvinyl chloride composition for removing formaldehyde, has excellent formaldehyde removal effect, and the formaldehyde removal rate can reach more than 90 percent at most; and
2. the polyvinyl chloride composition for removing formaldehyde according to the present invention produces an article for removing formaldehyde having a good odor grade.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It will be appreciated that other embodiments are contemplated and may be made without departing from the scope or spirit of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical and chemical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
With respect to car mats, which are the most common car products, there is currently a lack of an effective and long-term static formaldehyde adsorption product on the market. According to the technical scheme of the invention, the water-based formaldehyde adsorbent is mixed with PVC, then the modified polyvinyl chloride material with the formaldehyde removing effect is obtained according to the PVC processing method, and the material can be used for manufacturing the automobile foot mat with excellent formaldehyde removing effect and good odor grade.
According to a first aspect of the present invention, there is provided a polyvinyl chloride composition for removing formaldehyde, comprising, based on 100 parts by weight of the total weight of the composition:
30-60% by weight of a polyvinyl chloride resin;
25-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-5 wt% of an organic acid;
0.01-5 wt% of an alkylamine alcohol;
0.02-10 wt% of an organic solvent; and
0.03-15% by weight of water.
According to the technical scheme of the invention, a PVC resin material is adopted as a base material of the polyvinyl chloride composition for removing formaldehyde. The type and source of the polyvinyl chloride resin are not particularly limited, and it may be commercially available or prepared according to a known synthetic method. However, in order to satisfy processability and desired mechanical properties of the resulting article for removing formaldehyde, the weight average molecular weight of the polyvinyl chloride resin is 1000g/mol to 2000 g/mol. In order to achieve good formaldehyde removal effect and odor grade, the polyvinyl chloride resin content of the polyvinyl chloride composition for removing formaldehyde is 30 to 60% by weight. Preferably, the polyvinyl chloride resin is preferably polyvinyl chloride resin powder in order to facilitate sufficient mixing in the PVC processing. Commercially available products of polyvinyl chloride resin that can be used include: polyvinyl chloride resin products provided by Hangzhou plastics Co., Ltd have weight average molecular weights of 1000g/mol, 1600g/mol and 2000g/mol, respectively.
According to the technical scheme of the invention, the plasticizer is added into the polyvinyl chloride composition for removing formaldehyde to improve the plasticizing property of the product. The plasticizer is preferably an ester plasticizer. More preferably, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate or a mixture thereof. In order to achieve a good plasticizing effect, the content of the plasticizer in the polyvinyl chloride composition for removing formaldehyde is 25 to 50% by weight. Commercially available products of plasticizers that may be employed include: DINP (diisononyl phthalate) and DINCH (diisononyl cyclohexane 1, 2-dicarboxylate) supplied by BASF corporation.
According to the technical scheme of the invention, the filler is added into the polyvinyl chloride composition for removing formaldehyde to adjust the mechanical property of the polyvinyl chloride material prepared from the composition. Preferably, the filler is calcium carbonate. The content of the filler in the polyvinyl chloride composition for removing formaldehyde is 3-25 wt%.
According to the technical scheme of the invention, alkylamine alcohol is adopted as a formaldehyde removing agent in the polyvinyl chloride composition for removing formaldehyde. In order to obtain a good formaldehyde removing effect, the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure BDA0001713998950000081
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
Preferably, the alkylamine alcohol is selected from one or more of tromethamine, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol. Wherein tromethamine, serinol and 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol are compounds represented by the above-described formula (1), and [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol are compounds represented by the above-described formula (2). Commercially available products of alkylamine alcohols that can be employed include: FA-43 (tromethamine), FA-42H (serinol), FA-103 (4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol), FB-C2((9ci) - [ (2-aminoethyl) imino ] bis-methanol; CAS 623173-08-0), FB-C4((9ci) - [ (4-aminobutyl) imino ] bis-methanol; CAS 289045-27-8), manufactured by Shanghai Chongyao chemical company, and MEA (monoethanolamine), supplied by BASF company.
Preferably, in order to obtain good formaldehyde removal effect and odor grade, the content of alkylamine alcohol in the polyvinyl chloride composition for removing formaldehyde is 0.01 to 5% by weight, preferably 0.1 to 5% by weight, and more preferably 0.5 to 1% by weight. When the content of the alkylamine alcohol in the polyvinyl chloride composition for removing formaldehyde is less than 0.01 percent by weight, the obtained polyvinyl chloride material has poor formaldehyde removing effect and can not meet the grade requirement acceptable in the field; when the content of alkylamine alcohol in the polyvinyl chloride composition for removing formaldehyde is more than 5 wt%, the organic acid odor of the obtained polyvinyl chloride material is large and cannot meet the grade requirement acceptable in the field.
Preferably, the alkylamine alcohol is a mixture of the compound represented by formula (1) and the compound represented by formula (2) in order to obtain the best formaldehyde removal effect and odor level. More preferably, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the mixing weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is from 1: 4 to 4: 1, most preferably from 1: 2 to 2: 1. When a mixture of the compound represented by formula (1) and the compound represented by formula (2) is selected within the above-mentioned range and the weight ratio thereof is controlled within the range of 1: 4 to 4: 1, formaldehyde gas is minimized and volatile organic gas odor is minimized.
The alkylamine alcohol used according to the technical scheme of the invention is an aqueous solution obtained by dissolving the alkylamine alcohol in water, and due to the compatibility problem with the PVC resin, a uniform mixture can not be obtained when the alkylamine alcohol is mixed with a PVC resin system, and solid precipitates can be generated. Thus, the polyvinyl chloride composition for removing formaldehyde according to the present invention may further comprise an organic acid for improving the compatibility of the alkylamine alcohol with PVC. Preferably, the organic acid is C having 8 to 18 carbon atoms8-C18An organic acid. More preferably, C is8-C18The organic acid is at least one of caprylic acid and isostearic acid. In order to obtain good compatibility of the alkylamine alcohol with PVC, the polyvinyl chloride composition for removing formaldehyde comprises 0.01 to 5% by weight, preferably 0.1 to 1% by weight, of said organic acid, based on 100% by weight of the total weight thereof. In the preparation of the polyvinyl chloride composition for removing formaldehyde according to the present invention, the alkylamine alcohol is generally first mixed with the organic acid to obtain a premix, and then the premix is uniformly mixed with the remaining components such as PVC.
According to the technical scheme of the invention, in order to realize that the alkylamine alcohol is emulsified by organic acid to form a transparent solution which can be uniformly mixed with the polyvinyl chloride resin and the like, the polyvinyl chloride composition for removing formaldehyde further comprises an organic solvent and water. The alkylamine alcohol is generally in a solid form and is difficult to be uniformly mixed with components such as a polyvinyl chloride resin. According to an embodiment of the present invention, the alkylamine alcohol is first dissolved in water to form a liquid phase, and then an organic acid dissolved in an organic solvent is added to the liquid phase to emulsify the alkylamine alcohol, thereby forming a solution containing alkylamine alcohol. The solution containing alkylamine alcohol can be mixed well with the components of polyvinyl chloride resin and the like in the subsequent step.
Preferably, the solvent is an alcohol having 1 to 3 carbon atoms, and specific examples include, but are not limited to, Methanol (Methanol) or Isopropanol (IPA); or N-alkylpyrrolidone in which the number of carbon atoms of the alkyl group is 1 to 8, and N-methylpyrrolidone (NMP) is a specific example. The content of the solvent is not particularly limited as long as good mixing between the respective components can be achieved.
Preferably, the amount of the organic solvent is 0.02 to 10% by weight and the amount of water is 0.03 to 15% by weight, based on 100% by weight of the total weight of the polyvinyl chloride composition for removing formaldehyde.
In addition to the above listed components, other components may be included in the polyvinyl chloride composition for removing formaldehyde according to the present invention to improve various properties of the manufactured article, such as formability, color, mold release property, antibacterial property, flame retardancy, etc. Including but not limited to colorants, mold release agents, antioxidants, heat stabilizers, antimicrobial agents, flame retardants, and the like.
According to a second aspect of the present invention, there is provided an article for removing formaldehyde, comprising, based on 100 parts by weight of the total weight of the article:
40-60% by weight of a polyvinyl chloride resin;
30-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-6.67 wt% of an organic acid; and
0.01-6.67 wt% of alkylamine alcohol.
According to the technical scheme of the invention, the PVC resin material is used as the basic material of the product for removing formaldehyde. The type and source of the polyvinyl chloride resin are not particularly limited, and it may be commercially available or prepared according to a known synthetic method. However, in order to satisfy processability and desired mechanical properties of the resulting article for removing formaldehyde, the weight average molecular weight of the polyvinyl chloride resin is 1000g/mol to 2000 g/mol. In order to achieve good formaldehyde removal and odor levels, the polyvinyl chloride resin content of the article for removing formaldehyde is 40 to 60% by weight. Preferably, the polyvinyl chloride resin is preferably polyvinyl chloride resin powder in order to facilitate sufficient mixing in the PVC processing. Commercially available products of polyvinyl chloride resin that can be used include: polyvinyl chloride resin products provided by Hangzhou plastics Co., Ltd have weight average molecular weights of 1000g/mol, 1600g/mol and 2000g/mol, respectively.
According to the technical scheme of the invention, the plasticizer is added into the product for removing formaldehyde to improve the plasticizing property of the product. The plasticizer is preferably an ester plasticizer. More preferably, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate or a mixture thereof. In order to achieve a good plasticizing effect, the content of the plasticizer in the formaldehyde removal product is 30 to 50 wt%. Commercially available products of plasticizers that may be employed include: DINP (diisononyl phthalate) and DINCH (diisononyl cyclohexane 1, 2-dicarboxylate) supplied by BASF corporation.
According to the technical scheme of the invention, the filler is added into the product for removing formaldehyde to adjust the mechanical property of the polyvinyl chloride material prepared from the composition. Preferably, the filler is calcium carbonate. The content of the filler in the product for removing formaldehyde is 3-25 wt%.
According to the technical scheme of the invention, alkylamine alcohol is adopted as a formaldehyde removing agent in the product for removing formaldehyde. In order to obtain a good formaldehyde removing effect, the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure BDA0001713998950000111
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
Preferably, the alkylamine alcohol is selected from one or more of chlorobutanetriol, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol. Wherein tromethamine, serinol and 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol are compounds represented by the above-described formula (1), and [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol are compounds represented by the above-described formula (2). Commercially available products of alkylamine alcohols that can be employed include: FA-43 (tromethamine), FA-42H (serinol), FA-103 (4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol), FB-C2((9ci) - [ (2-aminoethyl) imino ] bis-methanol; CAS 623173-08-0), FB-C4((9C i) - [ (4-aminobutyl) imino ] bis-methanol; CAS 289045-27-8), manufactured by Shanghai Chongyao chemical company, and MEA (monoethanolamine), supplied by BASF company.
Preferably, in order to obtain good formaldehyde removal effect and odor grade, the content of alkylamine alcohol in the article for removing formaldehyde is 0.01 to 6.67 wt%, preferably 0.1 to 6.67 wt%, and more preferably 0.52 to 1.05 wt%. When the content of the alkylamine alcohol in the product for removing formaldehyde is less than 0.01 percent by weight, the obtained polyvinyl chloride material has poor formaldehyde removing effect and can not meet the grade requirement acceptable in the field; when the content of alkylamine alcohol in the formaldehyde-removing product is more than 6.67 wt%, the organic acid smell of the obtained polyvinyl chloride material is large, and the acceptable grade requirement in the field can not be achieved.
Preferably, the alkylamine alcohol is a mixture of the compound represented by formula (1) and the compound represented by formula (2) in order to obtain the best formaldehyde removal effect and odor level. More preferably, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the mixing weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is from 1: 4 to 4: 1, most preferably from 1: 2 to 2: 1. When a mixture of the compound represented by formula (1) and the compound represented by formula (2) is selected within the above-mentioned range and the weight ratio thereof is controlled within the range of 1: 4 to 4: 1, formaldehyde gas is minimized and volatile organic gas odor is minimized.
The alkylamine alcohol used according to the technical scheme of the invention is an aqueous compound, and due to the compatibility problem with the PVC resin, a uniform mixture can not be obtained when the alkylamine alcohol is mixed with a polyvinyl chloride resin system, and solid precipitates can be generated. Thus, according to the inventionThe article for removing formaldehyde comprises an organic acid for improving the compatibility of the alkylamine alcohol with PVC. Preferably, the organic acid is C having 8 to 18 carbon atoms8-C18An organic acid. More preferably, C is8-C18. The organic acid is at least one of caprylic acid and isostearic acid. In order to obtain good compatibility of the alkylamine alcohols with PVC, the polyvinyl chloride composition for removing formaldehyde comprises from 0.01 to 6.67% by weight, preferably from 0.1 to 1.05% by weight, of said organic acid, based on 100% by weight of the total weight of the polyvinyl chloride composition. In the preparation of the polyvinyl chloride composition for removing formaldehyde according to the present invention for preparing an article for removing formaldehyde, the alkylamine alcohol is generally first mixed with the organic acid to obtain a premix, and then the premix is uniformly mixed with the remaining components such as PVC.
In addition to the above listed components, other components may be included in the article for removing formaldehyde according to the present invention to improve various properties of the article to be manufactured, such as formability, color, mold release, antibacterial property, flame retardancy, etc. Including but not limited to colorants, mold release agents, antioxidants, heat stabilizers, antimicrobial agents, flame retardants, and the like.
According to the technical scheme of the invention, the product for removing formaldehyde comprises but is not limited to a foot pad, a ground mat or a packaging bag for use in an automobile.
According to a third aspect of the present invention, there is provided an article for removing formaldehyde, comprising a main body portion and a coating covering the main body portion, the coating comprising, based on 100% by weight of the total weight of the coating:
40-60% by weight of a polyvinyl chloride resin;
30-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-6.67 wt% of an organic acid; and
0.01-6.67 wt% of alkylamine alcohol.
The shape, material, size, etc. of the main body portion of the article for removing formaldehyde are not particularly limited, and may be specifically selected according to the actual application.
According to the technical scheme of the invention, a PVC resin material is adopted as a base material of a coating layer covering the main body part in the product for removing formaldehyde. The type and source of the polyvinyl chloride resin are not particularly limited, and it may be commercially available or prepared according to a known synthetic method. However, in order to satisfy the processability and the desired mechanical properties of the resulting article for removing formaldehyde, the weight average molecular weight of the polyvinyl chloride resin is 1000-2000. In order to achieve good formaldehyde removal and odor grade, the polyvinyl chloride resin content of the article for removing formaldehyde is 40 to 60% by weight. Preferably, the polyvinyl chloride resin is preferably polyvinyl chloride resin powder in order to facilitate sufficient mixing in the PVC processing. Commercially available products of polyvinyl chloride resin that can be used include: polyvinyl chloride resin products provided by Hangzhou plastics Co., Ltd have weight average molecular weights of 1000g/mol, 1600g/mol and 2000g/mol, respectively.
According to the technical scheme of the invention, the plasticizing property of the coating is improved by adding the plasticizer into the coating covering the main body part in the product for removing formaldehyde. The plasticizer is preferably an ester plasticizer. More preferably, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate or a mixture thereof. In order to achieve a good plasticizing effect, the content of the plasticizer in the formaldehyde removal product is 30 to 50 wt%. Commercially available products of plasticizers that may be employed include: DINP (diisononyl phthalate) and DINCH (diisononyl cyclohexane 1, 2-dicarboxylate) supplied by BASF corporation.
According to the technical scheme of the invention, the filler is added into the coating covering the main body part in the product for removing formaldehyde so as to adjust the mechanical property of the polyvinyl chloride material prepared from the composition. Preferably, the filler is calcium carbonate. The content of the filler in the coating layer covering the main body portion in the article for removing formaldehyde is 3 to 25% by weight.
According to the technical scheme of the invention, alkylamine alcohol is used as a formaldehyde removing agent in the coating. In order to obtain a good formaldehyde removing effect, the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure BDA0001713998950000141
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
Preferably, the alkylamine alcohol is selected from one or more of tromethamine, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol. Wherein tromethamine, serinol and 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol are compounds represented by the above-described formula (1), and [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol are compounds represented by the above-described formula (2). Commercially available products of alkylamine alcohols that can be employed include: FA-43 (tromethamine), FA-42H (serinol), FA-103 (4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol), FB-C2((9ci) - [ (2-aminoethyl) imino ] bis-methanol; CAS 623173-08-0), FB-C4((9ci) - [ (4-aminobutyl) imino ] bis-methanol; CAS 289045-27-8), manufactured by Shanghai Chongyao chemical company, and MEA (monoethanolamine), supplied by BASF company.
Preferably, in order to obtain good formaldehyde removal and odor levels, the alkylamine alcohol is present in the coating in an amount of from 0.01 to 6.67 wt.%, preferably from 0.1 to 6.67 wt.%, and more preferably from 0.52 to 1.05 wt.%. When the content of alkylamine alcohol in the coating is less than 0.01 wt%, the obtained polyvinyl chloride material has poor formaldehyde removal effect and cannot meet the grade requirement acceptable in the field; when the content of alkylamine alcohol in the coating layer is more than 6.67 wt%, the organic acid odor of the resulting polyvinyl chloride material is large, and cannot meet the grade requirement acceptable in the art.
Preferably, the alkylamine alcohol is a mixture of the compound represented by formula (1) and the compound represented by formula (2) in order to obtain the best formaldehyde removal effect and odor level. More preferably, in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the mixing weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is from 1: 4 to 4: 1, most preferably from 1: 2 to 2: 1. When a mixture of the compound represented by the formula (1) and the compound represented by the formula (2) is selected within the above-mentioned range and the weight ratio thereof is controlled within the range of 1: 4 to 4: 1, formaldehyde gas is minimized and volatile organic gas odor is minimized
The alkylamine alcohol used according to the technical scheme of the invention is an aqueous compound, and due to the compatibility problem with PVC, a uniform mixture cannot be obtained when the alkylamine alcohol is mixed with a polyvinyl chloride resin system, and solid precipitates are generated. Thus, the coating according to the invention comprises an organic acid for increasing the compatibility of the alkylamine alcohol with PVC. Preferably, the organic acid is C having 8 to 18 carbon atoms8-C18An organic acid. More preferably, C is8-C18The organic acid is at least one of caprylic acid and isostearic acid. In order to obtain good compatibility of the alkylamine alcohols with PVC, the polyvinyl chloride composition for removing formaldehyde comprises from 0.01 to 6.67% by weight, preferably from 0.1 to 1.05% by weight, of said organic acid, based on 100% by weight of the total weight of the polyvinyl chloride composition. In the preparation of the polyvinyl chloride composition for removing formaldehyde according to the present invention for preparing the coating layer, the alkylamine alcohol is generally first mixed with the organic acid to obtain a premix, and then the premix is uniformly mixed with the remaining components such as PVC.
In addition to the above listed components, other components may be included in the coating layer of the article for removing formaldehyde according to the present invention to improve various properties of the article to be manufactured, such as formability, color, mold release property, antibacterial property, flame retardancy, etc. Including but not limited to colorants, mold release agents, antioxidants, heat stabilizers, antimicrobial agents, flame retardants, and the like.
According to the technical scheme of the invention, the product for removing formaldehyde comprises but is not limited to a foot pad, a ground mat or a packaging bag for use in an automobile.
The article for removing formaldehyde according to the second aspect of the present invention as described above is prepared by the following method: the polyvinyl chloride composition for removing formaldehyde according to the first aspect of the present invention is extrusion-molded at a high temperature (150 ℃ or higher) through an extruder, and then cooled and cut into particles. The particles are then formed into the desired article shape by a forming process.
Further, the article for removing formaldehyde according to the third aspect of the present invention as described above, which comprises a main body portion and a coating layer covering the main body portion, is prepared by the following method: the polyvinyl chloride composition for removing formaldehyde according to the first aspect of the present invention is applied on a body part having a desired shape, followed by drying to remove an organic solvent and water, thereby forming a coating layer.
The present invention will be described in more detail with reference to examples. It should be noted that the description and examples are intended to facilitate the understanding of the invention, and are not intended to limit the invention. The scope of the invention is to be determined by the claims appended hereto.
Examples
In the present invention, unless otherwise indicated, all reagents used were commercially available products and were used without further purification treatment. Further, "%" mentioned is "% by weight", and "parts" mentioned is "parts by weight".
Test method
Various PVC articles prepared in examples and comparative examples were tested for formaldehyde removal and odor properties according to the specific methods listed below.
Formaldehyde removability
The formaldehyde removability was measured by the following procedure.
1. Cutting the test sample into dimensions of 10cm × 8 cm;
2. placing a blank polyvinyl chloride material sample into a prepared 10-liter bag, adding 4 liters of high-purity nitrogen, and then heating at 65 ℃ for 2 hours;
3. the volatilized gas in the bag was extracted with a sampler and then the concentration of formaldehyde in the gas was measured using a liquid chromatograph (Agi lens 1100, agilent technologies ltd.) and recorded as C1;
4. the procedure of 1 to 3 was repeated using the polyvinyl chloride articles prepared in the examples and comparative examples in place of the above-mentioned blank polyvinyl chloride material test piece, and the formaldehyde concentration was recorded as C2;
5. using the polyvinyl chloride articles prepared in examples and comparative examples together with a blank polyvinyl chloride material, the steps 1 to 3 were repeated, and a formaldehyde concentration of C3 was recorded; and
6. the formaldehyde removal concentration was calculated according to the following formula
The formaldehyde removal rate X ═ C1+ C2-C3)/(C1+ C2) × 100%
The evaluation criteria for formaldehyde removal were as follows:
performance rating Formaldehyde removal rate X%
1 X≥90
2 80≤X＜90
3 70≤X＜80
4 60≤X＜70
5 40≤X＜60
6 X＜40
With levels that are acceptable in the art being levels 1, 2 or 3.
Nature of smell
Various PVC articles prepared in examples and comparative examples were tested for odor properties by the following methods.
The PVC material was processed into sheets of 20X 20cm thickness of about 2-4 mm, and the sheets were placed on a flat test stand, smelled with a nose at a distance of 10cm from the sheets, and the number of test persons was 9 according to the sensory score, and the average value was taken as a measurement value. The test scores and criteria are as follows.
Odor grade Description of the smell
1 Almost tasteless way
2 Slight smell
3 Special smell can be obviously smelled, but can be accepted
4 Special smell can be obviously smelledTaste and unacceptable
5 Strong unacceptable odor
Among these, the level acceptable in the art is level 1 or level 2.
The product name, chemical name, and supplier of the specific raw materials employed in the present invention are as follows.
Figure BDA0001713998950000181
Example 1
0.01g of FA-43 was mixed with 0.03g of deionized water, and then 0.01g of OcA dissolved in 0.02g of IPA was added thereto to obtain a premix. This premix was uniformly mixed with 34.33g of DINCH, 46.5g of polyvinyl chloride resin powder having a weight average molecular weight of 1600g/mol, and 19.1g of calcium carbonate to obtain a polyvinyl chloride composition for removing formaldehyde. The composition of the polyvinyl chloride composition for removing formaldehyde is shown in table 1 below.
The obtained polyvinyl chloride composition for removing formaldehyde is extruded and molded at a high temperature by an extruder, then cooled, and cut into particles. The particles were shaped by a shaping process into a PVC article having a length of 120cm, a width of 100cm and a thickness of 1.5 cm.
In the above-described method for manufacturing PVC articles, the process steps of heating and extrusion may volatilize components such as deionized water and solvent, and the contents of the respective components in the final PVC article are shown in table 3 below.
The resulting PVC articles were tested for formaldehyde removal and odor performance according to the measurement methods described in detail above, and the test results are shown in table 3.
Examples 2 to 24
A polyvinyl chloride composition for removing formaldehyde was prepared according to a similar method to example 1, except that each component and its content were changed as shown in the following table 1 or 2. The composition of the polyvinyl chloride composition for removing formaldehyde is shown in the following table 1 or 2.
A PVC article was prepared from the polyvinyl chloride composition for removing formaldehyde according to a method similar to example 1. The contents of the individual components in the final PVC article are shown in tables 3 or 4 below.
The resulting PVC articles were tested for formaldehyde removal and odor performance according to the measurement methods described in detail above, and the test results are shown in table 3 or 4.
Figure BDA0001713998950000201
Figure BDA0001713998950000211
Figure BDA0001713998950000221
Figure BDA0001713998950000231
From the results of examples 1 to 24 above, it can be seen that by selecting the respective components and their contents within the scope of the present invention, PVC articles having good aldehyde-removing grade and odor grade can be obtained. In particular, from the results of examples 18 to 20 and 24, it is understood that when alkylamine alcohol is specifically selected as a mixture of the compound represented by formula (1) and the compound represented by formula (2) (i.e., a mixture of FA-103 and FB-C4) and the mixing weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is controlled to be 1: 4 to 4: 1, a PVC product having both of very excellent aldehyde-removing grade (1) and odor grade (1) can be obtained.
Comparative examples 1 to 3
In comparative examples 1 to 3, polyvinyl chloride compositions for removing formaldehyde were prepared according to a similar method to that of inventive example 1, except that the respective components and the contents thereof were changed. The compositions of the polyvinyl chloride compositions prepared in comparative examples 1 to 3 are shown in the following table 5. The contents of the respective components in the PVC articles prepared in comparative examples 1 to 3 are shown in table 6 below.
The resulting PVC articles were tested for formaldehyde removal and odor performance according to the measurement methods described in detail above, and the test results are shown in table 6.
For convenience of comparison, the respective components and their contents of the polyvinyl chloride composition for removing formaldehyde prepared according to the above example 13 are also shown in table 5.
In addition, for ease of comparison, the individual components in the PVC article prepared according to example 13 above, their amounts, and the results of formaldehyde removal rating and odor rating are also shown in table 6.
TABLE 5 respective Components and their contents of the polyvinyl chloride compositions for removing Formaldehyde prepared in comparative examples 1 to 3 and example 13
Figure BDA0001713998950000251
Table 6 individual components and their amounts in the PVC articles prepared in comparative examples 1-3 and example 13, and results of formaldehyde removal rating and odor rating
Figure BDA0001713998950000252
In comparative example 1, small amounts of alkylamine alcohol (0.005 wt%) and organic acid (0.005 wt%) were used. Due to the low amount of alkylamine alcohol, the grade difference of aldehyde removal (grade 4) cannot reach the level acceptable in the field.
In comparative example 2, a large amount of alkylamine alcohol (the content in the product is 7 wt%) and organic acid (the content in the product is 7 wt%) were used. Due to the presence of excessive alkylamine alcohol, although the grade (1) is excellent in removing aldehyde, the odor grade (3) of the PVC article is inferior, lower than the grade acceptable in the art, with a significant organic acid odor due to the presence of a large amount of organic acid.
In comparative example 3, a PVC article was prepared following the procedure of example 13, except that Monoethanolamine (MEA), a comparative compound commonly used for formaldehyde removal, was used in place of alkylamine alcohol FA-103. The results show that the PVC article produced according to comparative example 3 had a poor formaldehyde removal rate and had an aldehyde removal rating of only 4.
The above examples and comparative examples demonstrate that PVC articles manufactured from the polyvinyl chloride composition for removing formaldehyde according to the present invention have excellent formaldehyde removal effect and good odor grade.
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the purpose of limiting the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention, and the technical contents of the present invention as claimed are all described in the claims.

Claims (46)

1. A polyvinyl chloride composition for removing formaldehyde, comprising, based on 100 parts by weight of the total weight of the composition:
30-60% by weight of a polyvinyl chloride resin;
25-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-5 wt% of an organic acid;
0.01-5 wt% of an alkylamine alcohol;
0.02-10 wt% of an organic solvent; and
0.03-15% by weight of water.
2. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure FDA0001713998940000011
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
3. The polyvinyl chloride composition for removing formaldehyde according to claim 2, wherein the alkylamine alcohol is a mixture of the compound represented by formula (1) and the compound represented by formula (2).
4. The polyvinyl chloride composition for removing formaldehyde according to claim 3, wherein the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) in the mixture of the compound represented by formula (1) and the compound represented by formula (2) is 1: 4 to 4: 1.
5. The polyvinyl chloride composition for removing formaldehyde according to claim 3, wherein the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) in the mixture of the compound represented by formula (1) and the compound represented by formula (2) is 1: 2 to 2: 1.
6. The polyvinyl chloride composition for removing formaldehyde according to claim 2, wherein the alkylamine alcohol is selected from one or more of tromethamine, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol.
7. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the alkylamine alcohol is in an amount of 0.1 to 5% by weight, based on the total weight of the polyvinyl chloride composition for removing formaldehyde taken as 100% by weight.
8. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the alkylamine alcohol is in an amount of 0.5 to 1% by weight, based on the total weight of the polyvinyl chloride composition for removing formaldehyde taken as 100% by weight.
9. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the organic acid is C8-C18An organic acid.
10. The polyvinyl chloride composition for removing formaldehyde according to claim 9, wherein said C8-C18The organic acid is at least one of caprylic acid and isostearic acid.
11. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the polyvinyl chloride resin has a weight average molecular weight of 1000g/mol to 2000 g/mol.
12. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the polyvinyl chloride resin is polyvinyl chloride resin powder.
13. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the plasticizer is an ester plasticizer.
14. The polyvinyl chloride composition for removing formaldehyde according to claim 13, wherein the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate, or a mixture thereof.
15. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the organic solvent is N-alkylpyrrolidone in which the number of carbon atoms of the alkyl group is 1 to 8.
16. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the organic solvent is an alcohol having 1 to 3 carbon atoms.
17. An article for removing formaldehyde, the article for removing formaldehyde comprising, based on the total weight of the article taken as 100 parts by weight:
40-60% by weight of a polyvinyl chloride resin;
30-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-6.67 wt% of an organic acid; and
0.01-6.67 wt% of alkylamine alcohol.
18. The article for removing formaldehyde according to claim 17, wherein the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure FDA0001713998940000031
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
19. The article for removing formaldehyde according to claim 18, wherein the alkylamine alcohol is a mixture of the compound represented by formula (1) and the compound represented by formula (2).
20. The article for removing formaldehyde according to claim 19, wherein in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is from 1: 4 to 4: 1.
21. The article for removing formaldehyde according to claim 19, wherein in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1: 2 to 2: 1.
22. The article of claim 18, wherein the alkylamine alcohol is selected from one or more of tromethamine, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol.
23. The article for removing formaldehyde according to claim 17, wherein the alkylamine alcohol is present in an amount of 0.1 to 6.67% by weight, based on the total weight of the article for removing formaldehyde taken as 100% by weight.
24. The article for removing formaldehyde according to claim 17, wherein the alkylamine alcohol is in an amount of 0.52 to 1.05% by weight, based on the total weight of the article for removing formaldehyde of 100% by weight.
25. The article for removing formaldehyde according to claim 17, wherein the organic acid is C8-C18An organic acid.
26. The article for removing formaldehyde according to claim 25, wherein C is8-C18The organic acid is at least one of caprylic acid and isostearic acid.
27. The article for removing formaldehyde according to claim 17, wherein the polyvinyl chloride resin has a weight average molecular weight of 1000g/mol to 2000 g/mol.
28. The article for removing formaldehyde according to claim 17, wherein the polyvinyl chloride resin is polyvinyl chloride resin powder.
29. The article for removing formaldehyde according to claim 17, wherein the plasticizer is an ester plasticizer.
30. The article for removing formaldehyde according to claim 29, wherein the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate, or a mixture thereof.
31. The article for removing formaldehyde according to claim 17, which is a foot mat.
32. An article for removing formaldehyde, the article for removing formaldehyde comprising a body portion and a coating covering the body portion, the coating comprising, by weight of its total weight of 100:
40-60% by weight of a polyvinyl chloride resin;
30-50 wt% of a plasticizer;
3-25 wt% of a filler;
0.01-6.67 wt% of an organic acid; and
0.01-6.67 wt% of alkylamine alcohol.
33. The article for removing formaldehyde according to claim 32, wherein the alkylamine alcohol is a compound represented by the following formula (1) or a compound represented by the following formula (2):
Figure FDA0001713998940000041
wherein,
in the formula (1), R1、R2And R3Each independently selected from H, CH3Or (CH)2)mOH, wherein m is an integer of 1 to 3, and R1、R2And R3Is (CH)2)mOH；
In the formula (2), n is an integer of 2 to 4.
34. The article for removing formaldehyde according to claim 33, wherein the alkylamine alcohol is a mixture of the compound represented by formula (1) and the compound represented by formula (2).
35. The article for removing formaldehyde according to claim 34, wherein the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) in the mixture of the compound represented by formula (1) and the compound represented by formula (2) is 1: 4 to 4: 1.
36. The article for removing formaldehyde according to claim 34, wherein in the mixture of the compound represented by formula (1) and the compound represented by formula (2), the weight ratio of the compound represented by formula (1) to the compound represented by formula (2) is 1: 2 to 2: 1.
37. The article of claim 33, wherein the alkylamine alcohol is selected from one or more of tromethamine, serinol, 4-amino-4 (3-hydroxypropyl) -1, 7-heptanediol, [ (2-aminoethyl) imino ] bis-methanol and [ (4-aminobutyl) imino ] bis-methanol.
38. The article for removing formaldehyde according to claim 32, wherein the alkylamine alcohol is in an amount of 0.1-6.67 wt%, based on the total weight of the coating taken as 100 wt%.
39. The article for removing formaldehyde according to claim 32, wherein the alkylamine alcohol is in an amount of 0.52 to 1.05 wt%, based on the total weight of the coating taken as 100 wt%.
40. The article for removing formaldehyde according to claim 32, wherein the organic acid is C8-C18An organic acid.
41. According to the rightThe article for removing formaldehyde of claim 40, wherein the C is8-C18The organic acid is at least one of caprylic acid and isostearic acid.
42. The article for removing formaldehyde according to claim 32, wherein the polyvinyl chloride resin has a weight average molecular weight of 1000g/mol to 2000 g/mol.
43. The article for removing formaldehyde according to claim 32, wherein the polyvinyl chloride resin is polyvinyl chloride resin powder.
44. The article for removing formaldehyde according to claim 32, wherein the plasticizer is an ester plasticizer.
45. The article for removing formaldehyde according to claim 44, wherein the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane-1, 2-dicarboxylate, or a mixture thereof.
46. The article for removing formaldehyde according to claim 32, which is a foot mat.
CN201810706315.6A 2018-06-29 2018-06-29 Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde Active CN110655731B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201810706315.6A CN110655731B (en) 2018-06-29 2018-06-29 Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde
PCT/IB2019/055477 WO2020003215A1 (en) 2018-06-29 2019-06-27 Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde
TW108123127A TW202010787A (en) 2018-06-29 2019-07-01 Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810706315.6A CN110655731B (en) 2018-06-29 2018-06-29 Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde

Publications (2)

Publication Number Publication Date
CN110655731A true CN110655731A (en) 2020-01-07
CN110655731B CN110655731B (en) 2022-03-04

Family

ID=67928859

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810706315.6A Active CN110655731B (en) 2018-06-29 2018-06-29 Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde

Country Status (3)

Country Link
CN (1) CN110655731B (en)
TW (1) TW202010787A (en)
WO (1) WO2020003215A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111214951A (en) * 2020-02-28 2020-06-02 山东锦程地毯有限公司 Floor mat with toxic gas removal function and preparation method thereof
CN111644050A (en) * 2020-05-06 2020-09-11 江苏卓高环保科技有限公司 Formaldehyde removal purification material capable of releasing fragrance and application of formaldehyde removal purification material to formaldehyde removal purifier
WO2024168456A1 (en) * 2023-02-13 2024-08-22 Henkel Ag & Co. Kgaa A composition for removing aldehyde and removing odor, and a process for preparing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114797455A (en) * 2022-04-28 2022-07-29 云南菩丕实业有限公司 Automobile foot pad with harmful gas purification function

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5545760A (en) * 1978-09-28 1980-03-31 Toyota Central Res & Dev Lab Inc Ultraviolet-absorbing amino compound and coating and coated product containing the same
CN1479763A (en) * 2000-12-13 2004-03-03 ����ķ�ն���ϩ��Ӽ����޹�˾ Stabilizer system for stabilizing polymers containing halogen
CN1548164A (en) * 2003-05-22 2004-11-24 王永利 Formaldehyde absorbent and its prepn
JP2005015794A (en) * 2003-06-05 2005-01-20 Mitsubishi Plastics Ind Ltd Decorative film
WO2010056441A1 (en) * 2008-11-17 2010-05-20 Dow Global Technologies Inc. Methods for reducing airborne formaldehyde
US20110306695A1 (en) * 2010-05-11 2011-12-15 Akdeniz Kimya, Sanayi Ve Ticaret A.S. Tin-Free Stabilizer Composition
CN103030923A (en) * 2012-11-26 2013-04-10 山东泰德新能源有限公司 Formaldehyde scavenger 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
CN106009219A (en) * 2016-07-02 2016-10-12 青岛千帆高新技术有限公司 Improved environment-friendly floor bedding layer
CN107841071A (en) * 2018-01-08 2018-03-27 金华观瑞科技有限公司 A kind of PVC decorative Film

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5545760A (en) * 1978-09-28 1980-03-31 Toyota Central Res & Dev Lab Inc Ultraviolet-absorbing amino compound and coating and coated product containing the same
CN1479763A (en) * 2000-12-13 2004-03-03 ����ķ�ն���ϩ��Ӽ����޹�˾ Stabilizer system for stabilizing polymers containing halogen
CN1548164A (en) * 2003-05-22 2004-11-24 王永利 Formaldehyde absorbent and its prepn
JP2005015794A (en) * 2003-06-05 2005-01-20 Mitsubishi Plastics Ind Ltd Decorative film
WO2010056441A1 (en) * 2008-11-17 2010-05-20 Dow Global Technologies Inc. Methods for reducing airborne formaldehyde
US20110306695A1 (en) * 2010-05-11 2011-12-15 Akdeniz Kimya, Sanayi Ve Ticaret A.S. Tin-Free Stabilizer Composition
CN103030923A (en) * 2012-11-26 2013-04-10 山东泰德新能源有限公司 Formaldehyde scavenger 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
CN106009219A (en) * 2016-07-02 2016-10-12 青岛千帆高新技术有限公司 Improved environment-friendly floor bedding layer
CN107841071A (en) * 2018-01-08 2018-03-27 金华观瑞科技有限公司 A kind of PVC decorative Film

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
YANXIONG PAN，等: "Preparation and absorption behavior to organic pollutants of macroporous hydrophobic polyvinyl alcohol-formaldehyde sponges", 《RSC ADVANCES》 *
胡润华: "甲醛吸附剂的合成与表征及其吸附性能的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *
艾小红，等: "以白乳胶为基质甲醛吸附剂的研制与应用", 《广州化工》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111214951A (en) * 2020-02-28 2020-06-02 山东锦程地毯有限公司 Floor mat with toxic gas removal function and preparation method thereof
CN111214951B (en) * 2020-02-28 2022-08-26 山东锦程地毯有限公司 Floor mat with toxic gas removal function and preparation method thereof
CN111644050A (en) * 2020-05-06 2020-09-11 江苏卓高环保科技有限公司 Formaldehyde removal purification material capable of releasing fragrance and application of formaldehyde removal purification material to formaldehyde removal purifier
WO2024168456A1 (en) * 2023-02-13 2024-08-22 Henkel Ag & Co. Kgaa A composition for removing aldehyde and removing odor, and a process for preparing the same

Also Published As

Publication number Publication date
CN110655731B (en) 2022-03-04
TW202010787A (en) 2020-03-16
WO2020003215A1 (en) 2020-01-02

Similar Documents

Publication Publication Date Title
CN110655731B (en) Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde
CN107190521B (en) A kind of low smell PVC artificial leather and preparation method thereof
CN103724799B (en) A kind of low smell, low diffusion polypropylene composition and preparation method thereof
US8637427B2 (en) Adsorptive composition and adsorptive molded article
JP7479477B2 (en) Low odor soft PVC material
CN103254499A (en) Low-smell vehicle polypropylene composite material and its preparation method
EP2976384A2 (en) "thermoplastic polymer formulation containing recycled polyolefins and method of preparing"
DE102015215152A1 (en) Rubber compound and vehicle tires
KR101509845B1 (en) Master batch, process for production thereof, and process for production of molded articles
JP2019090009A (en) Antifogging agent for polyolefin-based resin and use thereof
CN109957172A (en) A kind of eliminating smell agent, it is low distribute, automobile interior decoration polypropylene material resistant to high temperature and preparation method thereof
CN108524989B (en) Sterilizing and deodorizing agent for vehicle air conditioner
CN114874548A (en) Low-odor and low-emission composite polypropylene material for vehicles and preparation method thereof
KR101379619B1 (en) Thermoplastic polyetherester elastomer composition and elastic monofilament produced by the same
KR101010589B1 (en) Resin molded article emitting fragrance and method for manufacturing the same, pellet and composition for manufacturing the resin molded article
CN105820472A (en) Preparation method and application of antistatic plastic bag material composition and plastic bag
CN111296419A (en) Nano zinc carriage bacteriostatic odor-removing spray and preparation method thereof
CN103483926B (en) A kind of Antimicrobial environment-friendlytransparent transparent nitro bright finish coat and preparation method thereof
JPH11293034A (en) Deordorizing resin composition
CN111500076B (en) Low-odor thermoplastic elastomer material for automotive interior and preparation method thereof
CN107383686A (en) A kind of slush moulding powder with fragrance and its application
CN104479344A (en) Preparation method of health-care polyamide composite material for vehicle
JP2012077247A (en) Silver-containing resin composition and method for producing the same
KR20160023173A (en) Aroma rubber composition and the preparing method thereof
KR101833462B1 (en) Functional embossing interior sheet and manufacturing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant