WO2020003215A1

WO2020003215A1 - Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde

Info

Publication number: WO2020003215A1
Application number: PCT/IB2019/055477
Authority: WO
Inventors: Xin Huo; Warren Wang; Steve Chen; Zhiyu Shi; Mengling LI; Bright XIANG; Tommy Yu; August HE; Randy JIANG
Original assignee: 3M Innovative Properties Company
Priority date: 2018-06-29
Filing date: 2019-06-27
Publication date: 2020-01-02
Also published as: CN110655731B; TW202010787A; CN110655731A

Abstract

The present invention provides a polyvinyl chloride composition for removing formaldehyde and a product for removing formaldehyde. Specifically, the present invention provides a polyvinyl chloride composition for removing formaldehyde. The polyvinyl chloride composition for removing formaldehyde comprises, based on the total weight thereof as 100% by weight: 30-60% by weight of a polyvinyl chloride resin, 25-50% by weight of a plasticizer, 3-25% by weight of a filler, 0.01-5% by weight of an organic acid, 0.01-5% by weight of an alkylamine alcohol, 0.02-10% by weight of an organic solvent and 0.03-15% by weight of water. Products for removing formaldehyde manufactured from the polyvinyl chloride composition for removing formaldehyde according to the present invention offer excellent formaldehyde removal effects and desirable odor grades.

Description

POLYVINYL CHLORIDE COMPOSITION FOR REMOVING FORMALDEHYDE AND PRODUCT FOR REMOVING FORMALDEHYDE

TECHNICAL FIELD

The present invention relates to the field of indoor or in-vehicle pollution control.

Specifically, the present invention relates 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 primary pollution sources in newly built houses. Various products for removing harmful gases such as formaldehyde have been developed to absorb or adsorb indoor harmful gas pollution.

In addition, automobile foot mats are common accessories in automobiles that can absorb water, collect dust, and eliminate dirt. Automobile foot mats can also effectively prevent moisture or dirt remaining on shoe soles from causing slippage between the clutch, brake and throttle; prevent safety hazards; and reduce the possibility of automobile interior contamination and damage. However, many organic gases such as formaldehyde and various VOC gases may be left over in new automobiles. Automobile foot mats can be provided that remove

formaldehyde and eliminate the frustration that is causes. In particular, automobile foot mats cover a large area in automobiles and have benefits for formaldehyde removal. However, foot mats with similar functionality are rarely available in the current market.

Current in-vehicle static products for removing formaldehyde are classified into two types: aerosol sprays and activated carbon bags. Some spray products contain titanium dioxide nano particles, which can quickly react with formaldehyde. Since formaldehyde volatilizes constantly, such aerosol sprays will quickly become ineffective. Many activated carbon bag products merely absorb formaldehyde by adsorption because these products use ordinary coconut shell activated carbon. In this case, desorption will occur when adsorption reaches saturation, thus causing formaldehyde concentrations to increase again.

Therefore, it is necessary to develop a product for indoor or in-vehicle pollution control that generates no organic gas odor and is capable of long term static formaldehyde adsorption.

SUMMARY

In light of the technical problem described above, the present invention provides a polyvinyl chloride composition for removing formaldehyde and a product for removing formaldehyde. The product for removing formaldehyde manufactured from the polyvinyl chloride composition for removing formaldehyde according to the present invention offers excellent formaldehyde removal effects and a desirable odor grade.

The present inventors have accomplished the present invention through intensive research.

According to one aspect of the present invention, a polyvinyl chloride composition for removing formaldehyde is provided. The polyvinyl chloride composition for removing formaldehyde comprises, based on the total weight thereof as 100% by weight:

30-60% by weight of a polyvinyl chloride resin;

25-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-5% by weight of an organic acid;

0.01-5% by weight of an alkylamine alcohol;

0.02-10% by weight of an organic solvent; and

0.03-15% by weight of water.

In some embodiments, the alkylamine alcohol is a compound represented by Formula (1) or a compound represented by Formula (2):

Formula (1) Formula (2) wherein

in Formula (1), Ri, R₂ and R₃ are each independently selected from H, CH₃ or

(CH₂)_mOH, wherein m is an integer from 1 to 3 and at least one of Ri, R₂ and R₃ is (CH₂)_mOH; and

in Formula (2), n is an integer from 2 to 4.

In some embodiments, the alkylamine alcohol is a mixture of the compound represented by Formula (1) and the compound represented by Formula (2). In some embodiments, the alkylamine alcohol is a mixture of the compound represented by Formula (1) and the compound represented by Formula (2), and the weight ratio of the compound represented by Formula (1) to the compound represented by Formula (2) ranges from 1 :4 to 4: 1.

In some embodiments, the alkylamine alcohol is a mixture of the compound represented by Formula (1) and the compound represented by Formula (2), and the weight ratio of the compound represented by Formula (1) to the compound represented by Formula (2) ranges from 1 :2 to 2: 1.

In some embodiments, the alkylamine alcohol is one or a plurality of compounds selected from aminobutanetriol, serinol, 4-amino-4-(3-hydroxypropyl)-l,7-heptanediol, [(2- aminoethyl)imino]bis-methanol and [(4-aminobutyl)imino]bis-methanol.

In some embodiments, the amount of the alkylamine alcohol is 0.1-5% by weight based on the total weight of the polyvinyl chloride composition for removing formaldehyde as 100% by weight.

In some embodiments, the amount of the alkylamine alcohol is 0.5-1% by weight based on the total weight of the polyvinyl chloride composition for removing formaldehyde as 100% by weight.

In some embodiments, the organic acid is a CVC ix organic acid.

In some embodiments, the CVC ix organic acid is at least one of an octanoic acid and an isooctadecanoic acid.

In some embodiments, the weight-average molecular weight of the polyvinyl chloride resin is 1000 g/mol - 2000 g/mol.

In some embodiments, the polyvinyl chloride resin is a polyvinyl chloride resin powder.

In some embodiments, the plasticizer is an ester plasticizer.

In some embodiments, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane- 1, 2-diformate or a mixture thereof.

In some embodiments, the filler is a calcium carbonate.

In some embodiments, the polyvinyl chloride composition for removing formaldehyde further comprises a solvent.

In some embodiments, the solvent is A'-alkyl pyrrolidone, wherein the carbon atom number of the alkyl is 1-8.

In some embodiments, the solvent is an alcohol with a carbon atom number of 1-3. According to another aspect of the present invention, a product for removing formaldehyde is provided. The product for removing formaldehyde comprises, based on the total weight thereof as 100% by weight:

40-60% by weight of a polyvinyl chloride resin;

30-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-6.67% by weight of an organic acid; and

0.01-6.67% by weight of an alkylamine alcohol.

In some embodiments, the alkylamine alcohol is a compound represented by the following Formula (1) or a compound represented by the following Formula (2):

Formula (1) Formula (2) wherein

(CH₂)_mOH, wherein m is an integer from 1 to 3 and at least one of Ri, R₂ and R₃ is (CH₂)_mOH; in Formula (2), n is an integer from 2 to 4.

In some embodiments, the alkylamine alcohol is a mixture of the compound represented by Formula (1) and the compound represented by Formula (2).

In some embodiments, the alkylamine alcohol is a mixture of the compound represented by Formula (1) and the compound represented by Formula (2), and the weight ratio of the compound represented by Formula (1) to the compound represented by Formula (2) ranges from 1 :4 to 4: 1.

In some embodiments, the alkylamine alcohol is one or a plurality of compounds selected from aminobutanetriol, serinol, 4-amino-4-(3-hydroxypropyl)-l,7-heptanediol, [(2- aminoethyl)imino]bis-methanol and [(4-aminobutyl)imino]bis-methanol. In some embodiments, the amount of the alkylamine alcohol is 0.1-6.67% by weight based on the total weight of the product for removing formaldehyde as 100% by weight.

In some embodiments, the amount of the alkylamine alcohol is 0.52-1.05% by weight based on the total weight of the product for removing formaldehyde as 100% by weight.

In some embodiments, the organic acid is a CVC ix organic acid.

In some embodiments, the plasticizer is an ester plasticizer.

In some embodiments, the filler is a calcium carbonate.

In some embodiments, the product for removing formaldehyde is a foot mat.

According to still another aspect of the present invention, a product for removing formaldehyde is provided. The product for removing formaldehyde comprises a main body part and a coating covering the main body part. The coating comprises, based on the total weight thereof as 100% by weight:

40-60% by weight of a polyvinyl chloride resin;

30-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-6.67% by weight of an organic acid; and

0.01-6.67% by weight of an alkylamine alcohol.

Alternatively, the alkylamine alcohol is a compound represented by the following Formula (1) or a compound represented by the following Formula (2):

Formula (1) Formula (2) wherein

in Formula (1), Ri, R₂ and R₃ are each independently selected from H, CH₃ or (CH₂)_mOH, wherein m is an integer from 1 to 3 and at least one of Ri, R₂ and R₃ is (CH₂)_mOH; and

in Formula (2), n is an integer from 2 to 4.

In some embodiments, the amount of the alkylamine alcohol is 0.1-6.67% by weight based on the total weight of the coating as 100% by weight.

In some embodiments, the amount of the alkylamine alcohol is 0.52-1.05% by weight based on the total weight of the coating as 100% by weight.

In some embodiments, the organic acid is a CVC ix organic acid.

In some embodiments, the weight-average molecular weight of the polyvinyl chloride resin is 1000 g/mol - 2000 g/mol. In some embodiments, the polyvinyl chloride resin is a polyvinyl chloride resin powder.

In some embodiments, the plasticizer is an ester plasticizer.

In some embodiments, the filler is a calcium carbonate.

In some embodiments, the product for removing formaldehyde is a foot mat.

Compared with the prior art, the present invention has the following beneficial effects:

1. The product for removing formaldehyde manufactured from the polyvinyl chloride composition for removing formaldehyde according to the present invention offers excellent formaldehyde removal effects, with a formaldehyde removal rate reaching 90% or higher at maximum; and

2. the product for removing formaldehyde manufactured from the polyvinyl chloride composition for removing formaldehyde according to the present invention offers a desirable odor grade.

DETAILED DESCRIPTION

The present invention will be further described in detail below in conjunction with the embodiments. It will be appreciated that other embodiments are considered and can be implemented without departing from the scope or spirit of the present invention. Therefore, the following detailed description is non-limiting.

Unless otherwise specified, all numbers used in this description and the claims representing the characteristic sizes and quantities and physical properties should be understood as being modified by the term“approximately” under any and all circumstances. Therefore, unless stated to the contrary, parameters in numerical values listed in the above description and in the attached claims are all approximate values, and one skilled in the art is capable of seeking to obtain desired properties by taking advantage of contents of the teachings disclosed herein, and changing these approximate values appropriately. The use of a numeric value range represented by endpoints includes all numbers within such range and any range within such range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and etc.

Regarding automobile foot mats as the most common automobile accessory, an effective product capable of long-term static adsorption of formaldehyde is not currently available on the market. According to the technical solution of the present invention, a modified polyvinyl chloride material with an effect of removing formaldehyde can be obtained by mixing a water-based formaldehyde adsorbent with PVC and then adopting a PVC processing method. This material can be used to prepare automobile foot mats that offer excellent formaldehyde removal effects and good odor grades.

According to a first aspect of the present invention, the present invention provides a polyvinyl chloride composition for removing formaldehyde. The polyvinyl chloride composition for removing formaldehyde comprises, based on the total weight thereof as 100% by weight:

30-60% by weight of a polyvinyl chloride resin;

25-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-5% by weight of an organic acid;

0.01-5% by weight of an alkylamine alcohol;

0.02-10% by weight of an organic solvent; and

0.03-15% by weight of water.

According to the technical solution of the present invention, a PVC resin material is used as a base material of the polyvinyl chloride composition for removing formaldehyde. No special restrictions are imposed on the type and source of the polyvinyl chloride resin. The resin can be commercially purchased or prepared according to known synthetic methods. However, in order for the obtained formaldehyde-removing product to provide processability and the required mechanical properties, the weight-average molecular weight of the polyvinyl chloride resin is 1000 g/mol-2000 g/mol. In order to achieve good formaldehyde removal effects and a desirable odor grade, the content of the polyvinyl chloride resin in the polyvinyl chloride composition for removing formaldehyde is 30-60% by weight. Preferably, in order to facilitate sufficient mixing during PVC processing, the polyvinyl chloride resin is preferably a polyvinyl chloride resin powder. Commercially available polyvinyl chloride resin products which may be employed include: polyvinyl chloride resin products provided by Hangzhou Plastics Co., Ltd., which have weight-average molecular weights of 1000 g/mol, 1600 g/mol and 2000 g/mol, respectively.

According to the technical solution of the present invention, a plasticizer is added to the polyvinyl chloride composition for removing formaldehyde to improve the plasticizing properties of products. The plasticizer is preferably an ester plasticizer. More preferably, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane- 1, 2-diformate or a mixture thereof. In order to achieve good plasticizing effects, the content of the plasticizer in the polyvinyl chloride composition for removing formaldehyde is 25-50% by weight. Commercially available plasticizer products which may be employed include: DINP (diisononyl phthalate) and DINCH (diisononyl cyclohexane- 1, 2-diformate) provided by BASF Corporation.

According to the technical solution of the present invention, a filler is added to the polyvinyl chloride composition for removing formaldehyde to adjust the mechanical properties of polyvinyl chloride materials prepared from the composition. Preferably, the filler is a calcium carbonate. The content of the filler in the polyvinyl chloride composition for removing formaldehyde is 3-25% by weight.

According to the technical solution of the present invention, an alkylamine alcohol is used as a formaldehyde removal agent in the polyvinyl chloride composition for removing formaldehyde. In order to achieve good formaldehyde removal effects, the alkylamine alcohol is a compound represented by Formula (1) or a compound represented by Formula (2):

Formula (1) Formula (2)

wherein

in Formula (1), Ri, R and R are each independently selected from H, CEL or

(CH₂)_mOH, wherein m is an integer from 1 to 3 and at least one of Ri, R₂ and R is (CFD_mOFl; and

in Formula (2), n is an integer from 2 to 4.

Preferably, the alkylamine alcohol is one or a plurality of compounds selected from aminobutanetriol, serinol, 4-amino-4-(3-hydroxypropyl)-l,7-heptanediol, [(2-aminoethyl)imino]bis- methanol, and [(4-aminobutyl)imino]bis-methanol. The aminobutanetriol, serinol, and 4-amino-4-(3- hydroxypropyl)-l,7-heptanediol are compounds represented by Formula (1) above, and the [(2- aminoethyl)imino]bis-methanol and [(4-aminobutyl)imino]bis-methanol are compounds represented by Formula (2) above. Commercially available alkylamine alcohol products which may be employed include: FA-43 (aminobutanetriol), FA-42H (serinol), FA-103 (4-amino-4-(3-hydroxypropyl)-l,7- heptanediol), FB-C2 ((9ci)-[(2-aminoethyl)imino]bis-methanol; CAS 623173-08-0), and FB-C4 ((9ci)- [(4-aminobutyl)imino]bis-methanol; CAS 289045-27-8) produced by Shanghai Chongyao Chemical Co., Ltd., as well as MEA (monoethanolamine) provided by BASF Corporation. Preferably, in order to achieve good formaldehyde removal effects and a desirable odor grade, the content of the alkylamine alcohol in the polyvinyl chloride composition for removing formaldehyde is 0.01-5% by weight, preferably 0.1-5% by weight, and more preferably 0.5-1% by weight. When the content of the alkylamine alcohol in the polyvinyl chloride composition for removing formaldehyde is less than 0.01% by weight, an obtained polyvinyl chloride material has inferior formaldehyde removal effects and cannot meet the grade requirements acceptable in the art; when the content of the alkylamine alcohol in the polyvinyl chloride composition for removing formaldehyde is greater than 5% by weight, an obtained polyvinyl chloride material generates a strong organic acid odor and cannot meet the grade requirements acceptable in the art.

Preferably, in order to achieve optimal formaldehyde removal effects and odor grade, the alkylamine alcohol is a mixture of the compound represented by Formula (1) and the compound represented by Formula (2). 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) ranges from 1 :4 to 4: 1, and 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 scope described above and its weight ratio is controlled within the range from 1 :4 to 4: 1, formaldehyde gas is reduced to the lowest level and volatile organic gases generate the faintest odor.

The alkylamine alcohol employed according to the technical solution of the present invention is an aqueous solution obtained by dissolving the alkylamine alcohol in water. Due to compatibility issues with PVC resin, a uniform mixture usually cannot be obtained when the alkylamine alcohol is mixed with the polyvinyl chloride resin system, and solid precipitates will be generated from such mixture. Therefore, the polyvinyl chloride composition for removing formaldehyde according to the present invention can further comprise an organic acid for improving the compatibility between the alkylamine alcohol and the PVC. Preferably, the organic acid is a CV Ci₈ organic acid having 8-18 carbon atoms. More preferably, the CVC i x organic acid is at least one of an octanoic acid and an isooctadecanoic acid. In order to achieve good compatibility between the alkylamine alcohol and the PVC, the polyvinyl chloride composition for removing formaldehyde comprises 0.01-5% by weight, preferably 0.1-1% by weight of the organic acid based on the total weight of the polyvinyl chloride composition as 100% by weight. In preparation of the polyvinyl chloride composition for removing formaldehyde according to the present invention, usually the alkylamine alcohol and the organic acid are mixed first to obtain a premix, and then the premix is uniformly mixed with remaining components, such as the PVC. According to the technical solution of the present invention, the organic acid is used to emulsify the alkylamine alcohol so as to form a transparent solution that can be uniformly mixed with the polyvinyl chloride resin, etc. The polyvinyl chloride composition for removing formaldehyde further comprises an organic solvent and water. The alkylamine alcohol is typically in a solid form, and is therefore difficult to uniformly mix with other components, such as the polyvinyl chloride resin. According to the embodiments of the present invention, the alkylamine alcohol is first dissolved in the water to form a liquid phase, then the organic acid dissolved in the organic solvent is added to the liquid phase to emulsify the alkylamine alcohol so as to form a solution containing the alkylamine alcohol. The solution containing the alkylamine alcohol can be properly mixed with other components such as the polyvinyl chloride resin in subsequent steps.

Preferably, the solvent is an alcohol with a carbon atom number of 1-3, and specific examples include, but are not limited to, methanol or isopropanol (IPA); or the solvent is A- alkyl pyrrolidone, wherein the carbon atom number of the alkyl is 1-8, and a specific example is N- methyl pyrrolidone (NMP). No special restriction is imposed on the content of the solvent, as long as proper mixing between individual components can be achieved.

Preferably, the amount of the organic solvent is 0.02-10% by weight and the amount of the water is 0.03-15% by weight, based on the total weight of the polyvinyl chloride composition for removing formaldehyde as 100% by weight.

In addition to the components listed above, the polyvinyl chloride composition for removing formaldehyde according to the present invention can also comprise other components to improve various properties of products to be manufactured, including formability, color, demoldability, antibacterial properties, fire resistance, and etc. The other components include, but are not limited to, colorants, release agents, antioxidants, thermal stabilizers, antimicrobial agents, fire retardants, and etc.

According to a second aspect of the present invention, the present invention provides a product for removing formaldehyde. The product for removing formaldehyde comprises, based on the total weight thereof as 100% by weight:

40-60% by weight of a polyvinyl chloride resin;

30-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-6.67% by weight of an organic acid; and

0.01-6.67% by weight of an alkylamine alcohol. According to the technical solution of the present invention, a PVC resin material is used as a base material of the product for removing formaldehyde. No special restrictions are imposed on the type and source of the polyvinyl chloride resin, and the resin can be commercially purchased or prepared according to known synthetic methods. However, in order to meet mechanical properties needed for both processability and the obtained product for removing formaldehyde, the weight- average molecular weight of the polyvinyl chloride resin is 1000 g/mol - 2000 g/mol. In order to achieve good formaldehyde removal effects and a desirable odor grade, the content of the polyvinyl chloride resin in the product for removing formaldehyde is 40-60% by weight. Preferably, in order to facilitate sufficient mixing during PVC processing, the polyvinyl chloride resin is preferably a polyvinyl chloride resin powder. Commercially available polyvinyl chloride resin products which may be employed include: polyvinyl chloride resin products provided by Hangzhou Plastics Co., Ltd, which have weight-average molecular weights of 1000 g/mol, 1600 g/mol and 2000 g/mol, respectively.

According to the technical solution of the present invention, a plasticizer is added to the product for removing formaldehyde to improve the plasticizing properties of the product. The plasticizer is preferably an ester plasticizer. More preferably, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane- 1, 2-diformate or a mixture thereof. In order to achieve good plasticizing effects, the content of the plasticizer in the product for removing formaldehyde is 30-50% by weight. Commercially available plasticizer products which may be employed include: DINP (diisononyl phthalate) and DINCH (diisononyl cyclohexane- 1, 2-diformate) provided by BASF Corporation.

According to the technical solution of the present invention, a filler is added to the product for removing formaldehyde to adjust the mechanical properties of polyvinyl chloride materials prepared from the composition. Preferably, the filler is a calcium carbonate. The content of the filler in the product for removing formaldehyde is 3-25% by weight.

According to the technical solution of the present invention, an alkylamine alcohol is used as a formaldehyde removal agent in the product for removing formaldehyde. In order to achieve good formaldehyde removal effects, the alkylamine alcohol is a compound represented by Formula (1) or a compound represented by Formula (2):

Formula (1) Formula (2) wherein

in Formula (2), n is an integer from 2 to 4.

Preferably, the alkylamine alcohol is one or a plurality of compounds selected from aminobutanetriol, serinol, 4-amino-4-(3-hydroxypropyl)-l,7-heptanediol, [(2-aminoethyl)imino]bis- methanol and [(4-aminobutyl)imino]bis-methanol. The aminobutanetriol, serinol and 4-amino-4-(3- hydroxypropyl)-l,7-heptanediol are compounds represented by Formula (1) above, and [(2- aminoethyl)imino]bis-methanol and [(4-aminobutyl)imino]bis-methanol are compounds represented by Formula (2) above. Commercially available alkylamine alcohol products which may be employed include: FA-43 (aminobutanetriol), FA-42H (serinol), FA- 103 (4-amino-4-(3-hydroxypropyl)-l,7- heptanediol), FB-C2 ((9ci)-[(2-aminoethyl)imino]bis-methanol; CAS 623173-08-0), and FB-C4 ((9ci)-[(4-aminobutyl)imino]bis-methanol; CAS 289045-27-8) produced by Shanghai Chongyao Chemical Co., Ltd., as well as MEA (monoethanolamine) provided by BASF Corporation.

Preferably, in order to achieve good formaldehyde removal effects and a desirable odor grade, the content of the alkylamine alcohol in the product for removing formaldehyde is 0.01-6.67% by weight, preferably 0.1-6.67% by weight, and more preferably 0.52-1.05% by weight. When the content of the alkylamine alcohol in the product for removing formaldehyde is less than 0.01% by weight, an obtained polyvinyl chloride material has inferior formaldehyde removal effects and cannot meet the grade requirements acceptable in the art; when the content of the alkylamine alcohol in the product for removing formaldehyde is greater than 6.67% by weight, an obtained polyvinyl chloride material generates a strong organic acid odor and cannot meet the grade requirements acceptable in the art.

The alkylamine alcohol employed according to the technical solution of the present invention is an aqueous compound. Due to compatibility issues with PVC resin, a uniform mixture usually cannot be obtained when the alkylamine alcohol is mixed with the polyvinyl chloride resin system, and solid precipitates will be generated from such mixture. Therefore, the product for removing formaldehyde according to the present invention comprises an organic acid for improving the compatibility between the alkylamine alcohol and the PVC. Preferably, the organic acid is a CVCix organic acid having 8-18 carbon atoms. More preferably, the CVC ix organic acid is at least one of an octanoic acid and an isooctadecanoic acid. In order to achieve good compatibility between the alkylamine alcohol and the PVC, the polyvinyl chloride composition for removing formaldehyde comprises 0.01-6.67% by weight or preferably 0.1-1.05% by weight of the organic acid based on the total weight of the polyvinyl chloride composition as 100% by weight. In preparation of the product for removing formaldehyde based on the polyvinyl chloride composition for removing formaldehyde according to the present invention, usually the alkylamine alcohol and the organic acid are mixed first to obtain a premix, and then the premix is uniformly mixed with remaining components such as the PVC.

In addition to the components listed above, the product for removing formaldehyde according to the present invention can also comprise other components to improve various properties of the product to be manufactured, including formability, color, demoldability, antibacterial properties, fire resistance, and etc. The other components include, but are not limited to, colorants, release agents, antioxidants, thermal stabilizers, antimicrobial agents, fire retardants, and etc.

According to the technical solution of the present invention, the product for removing formaldehyde includes, but is not limited to, foot mats used in automobiles, floor mats or packaging bags.

According to a third aspect of the present invention, the present invention provides a product for removing formaldehyde. The product for removing formaldehyde comprises a main body part and a coating covering the main body part. The coating comprises, based on the total weight thereof as 100% by weight:

40-60% by weight of a polyvinyl chloride resin; 30-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-6.67% by weight of an organic acid; and

0.01-6.67% by weight of an alkylamine alcohol.

No special restrictions are imposed on the shape, material, size, and etc., of the main body part of the product for removing formaldehyde, which can be chosen specifically according to actual application conditions.

According to the technical solution of the present invention, a PVC resin material is used as a base material of the coating covering the main body part in the product for removing formaldehyde. No special restrictions are imposed on the type and source of the polyvinyl chloride resin, and the resin can be commercially purchased or prepared according to known synthetic methods However, in order to meet mechanical properties needed for both processability and the obtained product for removing formaldehyde, the weight-average molecular weight of the polyvinyl chloride resin is 1000-2000. In order to achieve good formaldehyde removal effects and a desirable odor grade, the content of the polyvinyl chloride resin in the product for removing formaldehyde is 40-60% by weight. Preferably, in order to facilitate sufficient mixing during PVC processing, the polyvinyl chloride resin is preferably a polyvinyl chloride resin powder. Commercially available polyvinyl chloride resin products which may be employed include: polyvinyl chloride resin products provided by Hangzhou Plastics Co., Ltd, which have weight-average molecular weights of 1000 g/mol, 1600 g/mol and 2000 g/mol, respectively.

According to the technical solution of the present invention, a plasticizer is added to the coating covering the main body part in the product for removing formaldehyde to improve the plasticizing properties of the coating. The plasticizer is preferably an ester plasticizer. More preferably, the ester plasticizer is diisononyl phthalate, diisononyl cyclohexane- 1, 2-diformate or a mixture thereof. In order to achieve good plasticizing effects, the content of the plasticizer in the product for removing formaldehyde is 30-50% by weight. Commercially available plasticizer products which may be employed include: DINP (diisononyl phthalate) and DINCH (diisononyl cyclohexane- 1, 2-diformate) provided by BASF Corporation.

According to the technical solution of the present invention, a filler is added to the coating covering the main body part in the product for removing formaldehyde to adjust the mechanical properties of polyvinyl chloride materials prepared from the composition. Preferably, the filler is a calcium carbonate. The content of the filler in the coating covering the main body part in the product for removing formaldehyde is 3-25% by weight. According to the technical solution of the present invention, an alkylamine alcohol is used as a formaldehyde removal agent in the coating. In order to achieve good formaldehyde removal effects, the alkylamine alcohol is a compound represented by Formula (1) or a compound represented by Formula (2):

Formula (1) Formula (2) wherein

in Formula (1), Ri, R and R are each independently selected from H, CEL or

in Formula (2), n is an integer from 2 to 4.

Preferably, in order to achieve good formaldehyde removal effects and a desirable odor grade, the content of the alkylamine alcohol in the coating is 0.01-6.67% by weight, preferably 0.1-6.67% by weight, and more preferably 0.52-1.05% by weight. When the content of the alkylamine alcohol in the coating is less than 0.01% by weight, an obtained polyvinyl chloride material has inferior formaldehyde removal effects and cannot meet the grade requirements acceptable in the art; when the content of the alkylamine alcohol in the coating is greater than 6.67% by weight, an obtained polyvinyl chloride material generates a strong organic acid odor and cannot meet the grade requirements acceptable in the art. Preferably, in order to achieve optimal formaldehyde removal effects and odor grade, the alkylamine alcohol is a mixture of the compound represented by Formula (1) and the compound represented by Formula (2). 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) ranges from 1 :4 to 4: 1, and 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 scope described above and its weight ratio is controlled within the range from 1 :4 to 4: 1, formaldehyde gas is reduced to the lowest level and volatile organic gases generate the faintest odor.

The alkylamine alcohol employed according to the technical solution of the present invention is an aqueous compound. Due to compatibility issues with PVC, a uniform mixture usually cannot be obtained when the alkylamine alcohol is mixed with a polyvinyl chloride resin system, and solid precipitates will be generated from such mixture. Therefore, the coating according to the present invention comprises an organic acid for improving the compatibility between the alkylamine alcohol and the PVC. Preferably, the organic acid is a CVCix organic acid having 8-18 carbon atoms. More preferably, the CVCix organic acid is at least one of an octanoic acid and an isooctadecanoic acid. In order to achieve good compatibility between the alkylamine alcohol and the PVC, the polyvinyl chloride composition for removing formaldehyde comprises 0.01-6.67% by weight or preferably 0.1- 1.05% by weight of the organic acid based on the total weight of the polyvinyl chloride composition as 100% by weight. In preparation of the polyvinyl chloride composition for removing formaldehyde of the coating according to the present invention, usually the alkylamine alcohol and the organic acid are mixed first to obtain a premix, and then the premix is uniformly mixed with remaining components such as the PVC.

In addition to the components listed above, the coating of the product for removing formaldehyde according to the present invention can also comprise other components to improve various properties of the product to be manufactured, including formability, color, demoldability, antibacterial properties, fire resistance, and etc. The other components include, but are not limited to, colorants, release agents, antioxidants, thermal stabilizers, antimicrobial agents, fire retardants, and etc.

The product for removing formaldehyde according to the second aspect of the present invention is prepared by the following method: using an extruder, extrusion molding of the polyvinyl chloride composition for removing formaldehyde according to the first aspect of the present invention at a high temperature (above l50°C), followed by cooling and cutting the molding into particles, and subsequently forming the particles into a required product shape through a forming process.

In addition, the product for removing formaldehyde comprising the main body part and the coating covering the main body part according to the third aspect of the present invention is prepared by the following method: applying the polyvinyl chloride composition for removing formaldehyde according to the first aspect of the present invention onto the main body part that has a required shape, and subsequently drying the polyvinyl chloride composition to remove the organic solvent and water so as to form the coating.

Hereinafter, the present invention is described in detail by way of embodiments. It is to be understood that the description and embodiments are intended to be illustrating, rather than limiting the present invention. The scope of the present invention is defined by the appended claims.

EXAMPLES

In the present invention, unless otherwise indicated, the used reagents are all commercially available and are used directly without further purification. Further, the“%” mentioned is“wt%”, and the“parts” mentioned are“parts by weight.”

Test Methods

The formaldehyde removal capability and odor of various PVC products prepared in the examples and comparative examples are tested according to the specific methods listed below.

Formaldehyde Removal Capability

Formaldehyde removal capability is measured through the following steps:

1. Cut a test sample into a size of 10 cm ^c 8 cm;

2. place the blank polyvinyl chloride material sample into a prepared 10 L bag, pump 4 L of high-purity nitrogen into the bag, and then heat it for 2 hours at 65 °C;

3. use a sampler to extract the volatile gases from the bag, then use a liquid chromatograph (Agilent 1100, Agilent Technologies Co., Ltd.) to test the formaldehyde concentration in the gas, and record a formaldehyde concentration as Cl;

4. substitute the blank polyvinyl chloride material sample with a polyvinyl chloride product prepared in the examples and comparative examples, repeat steps 1 to 3, and record a formaldehyde concentration as C2; 5. use a polyvinyl chloride product prepared in the examples and comparative examples and a blank polyvinyl chloride material together, repeat steps 1 to 3, and record a formaldehyde concentration as C3; and

6. calculate a formaldehyde removal concentration according to the following Formula:

Formaldehyde removal rate X = (Cl + C2 - C3) / (Cl + C2) ^c 100%

The criteria for evaluation of the formaldehyde removal rate is as follows:

A grade acceptable in the art is Grade 1, Grade 2 or Grade 3.

Odor

The odor of various PVC products prepared in the examples and comparative examples is tested through the following method: processing a PVC product material into a 20 cm ^c 20 cm sheet with a thickness of approximately 2-4 mm, then placing the sheet onto a flat test bench, smelling its odor with the nose at a distance of 10 cm from the sheet, and rating it based on the sense of smell, choosing the number of test participants as 9, and using their average value as a measured value.

The test rating grades and criteria are as follows:

A grade acceptable in the art is Grade 1 or Grade 2.

Materials

The product names, chemical names, and suppliers of the specific raw materials employed in the present invention are as follows:

Product name Chemical Name Supplier

OcA Octanoic acid Shanghai Jiarong Trading Co., Ltd.

CaA Isooctadecanoic acid Shanghai Jiarong Trading Co., Ltd.

DINP Diisononyl phthalate BASF

DINCH Diisononyl cyclohexane- 1 ,2-diformate BASF

FA-43 Aminobutanetriol Shanghai Chongyao Chemical

FA-42H Serinol Shanghai Chongyao Chemical

FA- 103 4-amino-4-(3 -hydroxypropyl)- 1 ,7-heptanediol Shanghai Chongyao Chemical

FB-C2 (9ci)-[(2-aminoethyl)imino]bis-methanol Shanghai Chongyao Chemical

FB-C4 (9ci)-[(4-aminobutyl)imino]bis-methanol Shanghai Chongyao Chemical

MEA Monoethanolamine BASF

IPA i-propanol Sinopharm Chemical Reagent Co., Ltd.

NMP A- methyl pyrrobdone Shanghai Jiarong Trading Co., Ltd.

NOP A-octyl pyrrobdone Sinopharm Chemical Reagent Co., Ltd.

Methanol Methanol Sinopharm Chemical Reagent Co., Ltd.

PVC 1000 PVC masterbatch Hangzhou Plastics Co., Ltd.

PVC 1600 PVC masterbatch Hangzhou Plastics Co., Ltd.

PVC 2000 PVC masterbatch Hangzhou Plastics Co., Ltd.

Calcium

Calcium carbonate Hangzhou Plastics Co., Ltd. carbonate

DI Water Deionized water 3M China Co., Ltd. R&D Center

Example 1

0.01 g of FA-43 was mixed with 0.03 g of deionized water, and 0.01 g of OcA dissolved in 0.02 g of IPA was then added to the mixture to obtain a premix. The premix was uniformly mixed with 34.33 g of DINCH, 46.5 g of a polyvinyl chloride resin powder having a weight-average molecular weight of 1600 g/mol and 19.1 g of a 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 was extrusion molded at a high temperature using an extruder, followed by cooling and cutting the mold into particles. Through a forming process, the particles were formed into a PVC product that is 120 cm long, 100 cm wide and 1.5 cm thick.

In the method for producing the PVC product described above, process steps such as heating and extruding will allow components such as the deionized water and the solvent to volatilize. The content of each component in the final PVC product is shown in Table 3 below.

The formaldehyde removal capability and odor of the obtained PVC product was tested according to the measurement methods described in detail above. The test results are shown in Table 3. Examples 2-24

Polyvinyl chloride compositions for removing formaldehyde were prepared according to the method similar to that of Example 1, with differences in individual components and their content changed as shown in Table 1 or 2 below. The compositions of the polyvinyl chloride compositions for removing formaldehyde are shown in Table 1 or 2 below.

PVC products were prepared using the polyvinyl chloride compositions for removing formaldehyde according to the method similar to that of Example 1. The content of each component in the final PVC products is shown in Table 3 or 4 below.

The formaldehyde removal capability and odor of the obtained PVC products were tested according to the measurement methods described in detail above. The test results are shown in Table 3 or 4.

Table 1. Components and their content in polyvinyl chloride compositions for removing formaldehyde prepared in Examples 1 -12

Table 2. Components and their content in polyvinyl chloride compositions for removing formaldehyde prepared in Examples 13-24

Table 3. Components and their content in PVC products prepared in Examples 1-12, and results of formaldehyde removal grades and odor grades thereof

Table 4. Components and their content in PVC products prepared in Examples 13-24, and results of formaldehyde removal grades and odor grades thereof

It can be known based on the results of the Examples 1-24 above that PVC products offering good formaldehyde removal grades and odor grades can be obtained by selecting components and their content within the scope of the present invention. In particular, it can be known from the results of Examples 18-20 and 24 that, when a mixture of the compound represented by Formula (1) and the compound represented by Formula (2) (namely, a mixture of FA- 103 and FB-C4) is particularly selected as analkylamine alcohol and the mixing weight ratio of the compound represented by Formula (1) to the compound represented by Formula (2) is controlled to be from 1:4 to 4: 1, a PVC product having both an excellent formaldehyde removal grade (1) and odor grade (1) can be obtained.

Comparative Examples 1-3

In Comparative Examples 1-3, polyvinyl chloride compositions for removing formaldehyde were prepared according to a similar method to that of Example 1 of the present invention, with differences in changes of components and their content. The compositions of the polyvinyl chloride compositions prepared in Comparative Examples 1-3 are shown in Table 5 below. The content of the components in the PVC products prepared in Comparative Examples 1-3 is shown in Table 6 below.

The formaldehyde removal capability and odor of the obtained PVC products were tested according to the measurement methods described in detail above. The test results are shown in Table 6.

For ease of comparison, the components and their content in the polyvinyl chloride composition for removing formaldehyde prepared according to Example 13 above are also shown in Table 5.

In addition, for ease of comparison, the components and their content in the PVC product prepared according to Example 13 above, as well as results of formaldehyde removal grade and odor grade thereof, are also shown in Table 6.

Table 5. Components and their content in polyvinyl chloride compositions for removing formaldehyde prepared in Comparative Examples 1-3 and Example 13

Table 6. Components and their content in PVC products prepared in Comparative Examples 1-3 and Example 13, and results of formaldehyde removal grades and odor grades thereof

In Comparative Example 1, small amounts of an alkylamine alcohol (0.005% by weight) and an organic acid (0.005% by weight) were used. Because the amount of the alkylamine alcohol is small, the formaldehyde removal grade is low (Grade 4), failing to reach the grade acceptable in the art.

In Comparative Example 2, large amounts of an alkylamine alcohol (the content of which in the product is 7% by weight) and an organic acid (the content of which in the product is 7% by weight) were used. Due to the presence of the excessive alkylamine alcohol, the formaldehyde removal grade (1) is superior. However, due to the presence of the large amount of the organic acid, the PVC product has a poor odor grade (3), which is lower than the grade acceptable in the art, and releases an obvious organic acid odor.

In Comparative Example 3, the PVC product was prepared according to the method in Example 13, with a difference in that the comparative compound monoethanolamine (MEA) that is usually used for removing formaldehyde was used in place of the alkylamine alcohol FA- 103. As shown in the results, the PVC product manufactured according to Comparative Example 3 has quite a low formaldehyde removal rate and only reaches a formaldehyde removal grade of 4.

As demonstrated by the above Examples and comparative examples, the PVC products manufactured from the polyvinyl chloride composition for removing formaldehyde according to the present invention offer excellent formaldehyde removal effects and desirable odor grades.

The embodiments of the present invention described above are merely illustrative of the preferred embodiments of the present invention, and are not intended to limit the concept and scope of the present invention. Various modifications and improvements can be made to the technical solution of the present invention by those skilled in the art without departing from the scope of the present invention, which are all embraced in the protection scope of the present invention as defined by appended claims.

Claims

1. A polyvinyl chloride composition for removing formaldehyde, the polyvinyl chloride composition for removing formaldehyde comprising, based on the total weight thereof as 100% by weight:

30-60% by weight of a polyvinyl chloride resin;

25-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-5% by weight of an organic acid;

0.01-5% by weight of an alkylamine alcohol;

0.02-10% by weight 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 Formula (1), a compound represented by Formula (2), or a mixture thereof:

Formula (1) Formula (2) wherein

in Formula (1), Ri, R and R are each independently selected from H, CFL or (CFL)_mOF[, wherein m is an integer from 1 to 3 and at least one of Ri, R_2, and R is (CFL)_mOF[; and

in Formula (2), n is an integer from 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), and the weight ratio of the compound represented by Formula (1) to the compound represented by Formula (2) ranges from 1 :4 to 4: 1.

4. The polyvinyl chloride composition for removing formaldehyde according to claim 2, wherein the alkylamine alcohol is one or a plurality of compounds selected from aminobutanetriol, serinol, 4- amino-4-(3-hydroxypropyl)-l,7-heptanediol, [(2-aminoethyl)imino]bis-methanol, and [(4- aminobutyl)imino]bis-methanol .

5. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the organic acid is at least one of an octanoic acid and an isooctadecanoic acid.

6. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the weight-average molecular weight of the polyvinyl chloride resin is 1000 g/mol-2000 g/mol.

7. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the polyvinyl chloride resin is a polyvinyl chloride resin powder.

8. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the plasticizer is diisononyl phthalate, diisononyl cyclohexane- 1, 2-diformate or a mixture thereof.

9. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the organic solvent is A'-alkyl pyrrolidone, and the carbon atom number of the alkyl is 1-8.

10. The polyvinyl chloride composition for removing formaldehyde according to claim 1, wherein the organic solvent is an alcohol with a carbon atom number of 1-3.

11. A product for removing formaldehyde, the product for removing formaldehyde comprising, based on the total weight thereof as 100% by weight:

40-60% by weight of a polyvinyl chloride resin;

30-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-6.67% by weight of an organic acid; and

0.01-6.67% by weight of an alkylamine alcohol.

12. The product for removing formaldehyde according to claim 11, wherein the alkylamine alcohol is a compound represented by Formula (1), a compound represented by Formula (2), or a mixture thereof:

Formula (1) Formula (2) wherein

in Formula (1), Ri, R₂ and R₃ are each independently selected from H, CH₃ or (CFh)_mOF[, wherein m is an integer from 1 to 3 and at least one of Ri, R₂ and R₃ is (CH₂)_mOH; and

in Formula (2), n is an integer from 2 to 4.

13. The product for removing formaldehyde according to claim 12, wherein the alkylamine alcohol is a mixture of the compound represented by Formula (1) and the compound represented by Formula (2), and the weight ratio of the compound represented by Formula (1) to the compound represented by Formula (2) ranges from 1:4 to 4: 1.

14. The product for removing formaldehyde according to claim 12, wherein the alkylamine alcohol is one or a plurality of compounds selected from aminobutanetriol, serinol, 4-amino-4-(3- hydroxypropyl)-l,7-heptanediol, [(2-aminoethyl)imino]bis-methanol and [(4- aminobutyl)imino]bis-methanol .

15. The product for removing formaldehyde according to claim 11, wherein the organic acid is at least one of an octanoic acid and an isooctadecanoic acid.

16. The product for removing formaldehyde according to claim 11, wherein the weight- average molecular weight of the polyvinyl chloride resin is 1000 g/mol - 2000 g/mol.

17. The product for removing formaldehyde according to claim 11, wherein the polyvinyl chloride resin is a polyvinyl chloride resin powder.

18. The product for removing formaldehyde according to claim 11 , wherein the plasticizer is diisononyl phthalate, diisononyl cyclohexane- 1, 2-diformate or a mixture thereof.

19. The product for removing formaldehyde according to claim 11, wherein the product for removing formaldehyde is a foot mat.

20. A product of any one of claims 11-19, wherein the product comprises a main body part and a coating covering the main body part, the coating comprising, based on the total weight thereof as 100% by weight:

40-60% by weight of a polyvinyl chloride resin;

30-50% by weight of a plasticizer;

3-25% by weight of a filler;

0.01-6.67% by weight of an organic acid; and

0.01-6.67% by weight of an alkylamine alcohol.