CN113583370A - Application of phenylboronic acid derivative - Google Patents
Application of phenylboronic acid derivative Download PDFInfo
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- CN113583370A CN113583370A CN202111010406.4A CN202111010406A CN113583370A CN 113583370 A CN113583370 A CN 113583370A CN 202111010406 A CN202111010406 A CN 202111010406A CN 113583370 A CN113583370 A CN 113583370A
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- acid derivative
- phenylboronic acid
- salt
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- toy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention provides an application of a phenylboronic acid derivative, wherein the phenylboronic acid derivative is used as an additive in an article. The additive of the phenylboronic acid derivative can generate a synergistic effect with a common additive borax, and can be used as a co-crosslinking agent on the premise of not influencing playability, so that the total boron content and the migratable boron content of soft mud such as schlemm, crystal mud, ultralight clay and the like and hydrogel toys are remarkably reduced, and the product meets the safety standard of the migratable boron content specified by the state.
Description
Technical Field
The invention relates to the field of chemical additives, in particular to application of a phenylboronic acid derivative.
Background
In recent years, soft mud and hydrogel toys are rapidly popularized in teenager groups and high-pressure groups, and have great potential safety hazards while being entertained and used for relieving pressure. Previously, most official media reveal that the migratable boron content in most soft mud and hydrogel toys on the market exceeds the standard, and some soft mud and hydrogel toys even exceed the safety standard by more than ten times, so that the health of consumers is seriously harmed.
The excessive boron element can be transferred and the addition density of the cross-linking agent borax is inseparable. In soft mud and hydrogel toys, polyvinyl alcohol (PVA) with a crosslinked structure is provided as a main playable component, and special playability which is difficult to replace is provided by crosslinking PVA with borax. Therefore, borax becomes a 'Sheng Fa Bao' for improving the product competitiveness of all manufacturers, and the addition amount is extremely high, so that the transferable boron content in the product exceeds the safety standard range specified by the state.
Borax (sodium tetraborate) may form a stable complex with PVA. In the early 90 s of the last century, foreign scholars conducted analytical studies on the crosslinking mechanism of inorganic boron by using Nuclear Magnetic Resonance (NMR) spectroscopy. The crosslinking process of boron crosslinkers is believed to involve hydrolysis of inorganic boron to borate ions and the borate ions form stable complexes with the ortho-cis hydroxyl groups in the vegetable gums as shown in the following formula:
aiming at the main structure PVA in the crystal mud, in addition to borax serving as a cross-linking agent, auxiliary chemical cross-linking agents can be selected, such as diisocyanate, dialdehyde, dianhydride and other types of compounds. However, compared with the complex of PVA-borax, PVA crosslinked by chemical reaction has a substantial change in its main structure, and becomes a real high molecular weight PVA rather than a dynamic crosslinked supramolecular structure of PVA-borax, resulting in complete disappearance of plasticity and increase of elasticity of the toy. The soft toys obtained after chemical crosslinking can not be accepted by consumers at home and abroad. The high-toxicity plasticizer, benzisothiazolinone and other additives are used to improve the plasticity of the product, but the effect is common, and the content of harmful substances in the product is far beyond the safety standard of the additives specified by the state.
Therefore, there is a need in the art for a new additive to address this problem.
Disclosure of Invention
In order to solve the problems of serious standard exceeding of boron content and poor playability in the existing soft mud and hydrogel toys, the invention aims to provide a phenylboronic acid derivative additive which can play a synergistic effect with borax to obviously improve the crosslinking effect of borax on a PVA (polyvinyl alcohol) component in the toys, thereby achieving the purposes of reducing the total boron content and the transferable boron content of products.
The invention adopts the following technical scheme to realize the purpose:
a) the phenylboronic acid derivative solid can be used, and can also be prepared into an aqueous solution, an organic solution or a mixed solvent solution;
b) in the blending preparation link of the soft mud and the hydrogel toy, the phenylboronic acid derivative solid or the prepared phenylboronic acid derivative solution is fully dispersed into the semi-finished product, so that the effect of auxiliary crosslinking is achieved.
The invention provides an application of a phenylboronic acid derivative, wherein the phenylboronic acid derivative is used as an additive in an article, and has a chemical structure shown as a general formula I:
wherein R is1-R5Selected from-H or-COOH and at least one of which contains-COOH; or the phenylboronic acid derivative is a salt with a chemical structure shown in a general formula I.
In a specific embodiment, the salt having a chemical structure shown in formula I includes an inorganic salt or an organic salt thereof, preferably one or more of a sodium salt, a potassium salt, a calcium salt, a magnesium salt, a lithium salt, a hydrochloride, a sulfate, and an ammonium salt thereof.
In a particular embodiment, the phenylboronic acid derivative is used as an additive to reduce the amount of borax used in an article, or to reduce the total boron content and/or the mobile boron content in an article.
In a specific embodiment, the phenylboronic acid derivative is applied in a location where it produces a synergistic effect with the additive borax.
In a specific embodiment, the phenylboronic acid derivative is applied to a low-boron soft mud or hydrogel toy, and preferably, the toy is one or more of Schlemm, bubble gum, Thladiant, pseudo water, crystal mud, liquid glass, space sand, light clay and plasticine.
In a specific embodiment, in the blending preparation link of the soft mud or hydrogel type toy, the phenylboronic acid derivative solid or the prepared phenylboronic acid derivative solution is fully dispersed into the toy semi-finished product, so that the effect of assisting crosslinking is achieved.
In a specific embodiment, when the phenylboronic acid derivative is used, the phenylboronic acid derivative is used directly in a solid state, or an aqueous solution of the phenylboronic acid derivative is used, or an organic solution of the phenylboronic acid derivative is used, or a mixed solvent solution of the phenylboronic acid derivative is used.
In a specific embodiment, the phenylboronic acid derivative solution is an aqueous solution thereof or a mixed solution prepared from one or more organic solvents selected from methanol, ethanol, glycerol, ethylene glycol, propylene glycol, isopropanol, N-propanol, acetone, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
In a specific embodiment, after the phenylboronic acid derivative is added, in order to achieve sufficient dispersion, heating and mixing operations are performed at a temperature of not higher than 120 ℃, preferably 60-80 ℃; the mixing time is 0-60min, preferably 10-30 min.
In a specific embodiment, the phenylboronic acid derivative accounts for 0.01-5% of the total mass of the article, the soft mud toy preferably accounts for 0.5-5%, and the hydrogel toy preferably accounts for 0.01-0.5%.
Compared with the prior art, the invention has the following beneficial effects:
1) the additive of the phenylboronic acid derivative provided by the invention has low toxicity, and LD50 is more than 3000 mg/kg.
2) The cross-linking agent borax has high toxicity, and the additive provided by the invention obviously improves the cross-linking effect of the borax by a synergistic effect, reduces the usage amount of the borax, and can control the total boron content and the transferable boron content of a product.
3) Compared with other chemical crosslinking means, the additive provided by the invention is the phenylboronic acid derivative, and the dynamic crosslinking characteristic of polyvinyl alcohol supermolecules in the toy is kept, so that the product still has high playability and can be generally accepted by the market.
In general, the water-soluble phenylboronic acid derivative additive provided by the invention can generate a synergistic effect with a common additive borax, and can be used as a co-crosslinking agent on the premise of not influencing playability, so that the transferable boron content of soft mud such as schlemm, crystal mud, ultralight clay and the like and hydrogel toys can be remarkably reduced, and the product meets the national safety standard of transferable boron content.
Detailed Description
The following examples are given as preferred embodiments of the present invention and are not intended to limit the scope of the present invention.
The raw materials used in the examples of the present invention are all commercially available.
Example 1
Example 1 is a low boron history lyme made using a phenylboronic acid derivative as an additive. Specifically, the method comprises the following steps:
preparing 10L of mixed liquid of PVA transparent liquid glue and 100mL of softener glycerol in a reaction kettle, raising the temperature in the mixture to 80 ℃, pouring 50g of 20 mass percent 2-carboxyl potassium phenylborate aqueous solution into the reaction kettle, stirring for 30min, dropwise adding 40g of sodium tetraborate saturated aqueous solution, continuing stirring for 30min, and discharging to obtain the low-boron Schlemm (a hydrogel toy) finished product. The detection is carried out by a third-party detection mechanism according to the national standard, and the following steps are known: the low boron Schlemm finished product had a migratable boron content of 240 mg/kg.
Comparative example 1
Comparative example 1 a conventional schlemm was made using a conventional method in the prior art. Specifically, the method comprises the following steps:
mixing 10L of PVA transparent liquid glue and 100mL of glycerin in a reaction kettle, raising the temperature in the mixture to 80 ℃, dropwise adding 1000g of sodium tetraborate saturated aqueous solution, stirring for 30min, and discharging to obtain a Schlemm finished product. The detection is carried out by a third-party detection mechanism according to the national standard, and the following steps are known: the migrating boron content of the finished product of the Schlemm is 1210 mg/kg.
The playability of the low boron schlemm prepared using the process of the present invention was consistent with the playability of the finished schlemm product of comparative example 1.
Example 2
Example 2 a low boron pseudo water was prepared using a phenylboronic acid derivative as an additive. Specifically, the method comprises the following steps:
preparing 10L of mixed liquid of PVA pseudo-hydrogel and 1L of glycerin in a reaction kettle, raising the temperature in the mixture to 60 ℃, pouring 60g of 20 mass percent 4-carboxyphenylboronic acid ethanol solution into the reaction kettle, stirring for 30min, dropwise adding 50g of sodium tetraborate saturated aqueous solution, continuing stirring for 30min, and discharging to obtain the low-boron pseudo-hydrogel finished product. The detection is carried out by a third-party detection mechanism according to the national standard, and the following steps are known: the transferable boron content of the finished low-boron pseudo water product is 280 mg/kg.
Comparative example 2
Comparative example 1 a general pseudo water was prepared using a conventional method in the prior art. Specifically, the method comprises the following steps:
mixing 10L of PVA pseudohydrogel and 1L of glycerol in a reaction kettle, raising the temperature in the mixture to 60 ℃, dropwise adding 1000g of saturated sodium tetraborate aqueous solution, stirring for 30min, and discharging to obtain a pseudohydrogel finished product. The detection is carried out by a third-party detection mechanism according to the national standard, and the following steps are known: the finished pseudo-water product had a migratable boron content of 1300 mg/kg.
The playability of the low boron pseudo-water prepared using the process of the present invention was consistent with the playability of the finished pseudo-water product of comparative example 2.
Example 3
Example 3 is a low boron history lyme made using a phenylboronic acid derivative as an additive. Specifically, the method comprises the following steps:
low-boron Schlemm's product was obtained by replacing the potassium 2-carboxyphenylborate in example 1 with an equivalent weight of 2-carboxyphenylboronic acid under otherwise the same conditions as in example 1. The playability of the schlemm product obtained in this example remained consistent with the schlemm product of example 1.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions and substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. Use of a phenylboronic acid derivative as an additive in an article, wherein the phenylboronic acid derivative has the chemical structure shown in formula I:
wherein R is1-R5Selected from-H or-COOH and at least one of which contains-COOH; or the phenylboronic acid derivative is a salt with a chemical structure shown in a general formula I.
2. The use according to claim 1, wherein the salt having a chemical structure represented by formula I comprises an inorganic salt or an organic salt thereof, preferably one or more of a sodium salt, a potassium salt, a calcium salt, a magnesium salt, a lithium salt, a hydrochloride salt, a sulfate salt, and an ammonium salt thereof.
3. Use according to claim 1, characterized in that the phenylboronic acid derivative is used as an additive for reducing the amount of borax used in an article, or for reducing the total boron content and/or the mobile boron content in an article.
4. Use according to claim 3, characterized in that the phenylboronic acid derivative is applied at a site where a synergistic effect with the additive borax occurs.
5. Use according to claim 1, wherein the phenylboronic acid derivative is used in a low-boron slush or hydrogel-type toy, preferably the toy is one or more of Schlemm, bubble gum, Peritai, pseudo water, crystal mud, liquid glass, space sand, light clay, and plasticine.
6. The use of claim 5, wherein the phenylboronic acid derivative solid or the prepared phenylboronic acid derivative solution is sufficiently dispersed into the toy semi-finished product in the blending preparation process of the soft mud or hydrogel toy, so as to achieve the effect of assisting crosslinking.
7. The use according to claim 6, wherein the phenylboronic acid derivative is used as it is in a solid state, or as an aqueous solution of the phenylboronic acid derivative, or as an organic solution of the phenylboronic acid derivative, or as a mixed solvent solution of the phenylboronic acid derivative.
8. The use according to claim 6, wherein the phenylboronic acid derivative solution is an aqueous solution thereof or a mixed solution prepared from one or more organic solvents selected from methanol, ethanol, glycerol, ethylene glycol, propylene glycol, isopropanol, N-propanol, acetone, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
9. The use according to claim 6, wherein, after the phenylboronic acid derivative is added, the heating and mixing operation is carried out at a temperature of not higher than 120 ℃, preferably 60-80 ℃ for achieving sufficient dispersion; the mixing time is 0-60min, preferably 10-30 min.
10. The use according to any one of claims 1 to 9, wherein the phenylboronic acid derivative accounts for 0.01-5% of the total weight of the article, preferably accounts for 0.5-5% of the soft mud toy, and preferably accounts for 0.01-0.5% of the hydrogel toy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111010406.4A CN113583370A (en) | 2021-08-31 | 2021-08-31 | Application of phenylboronic acid derivative |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111010406.4A CN113583370A (en) | 2021-08-31 | 2021-08-31 | Application of phenylboronic acid derivative |
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| CN113583370A true CN113583370A (en) | 2021-11-02 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694319A (en) * | 2016-01-18 | 2016-06-22 | 袁暾 | Medical polyvinyl alcohol gel and preparing method thereof |
| CN108948615A (en) * | 2018-08-28 | 2018-12-07 | 宁波百仕高联合工业有限公司 | A kind of nontoxic crystal mud of intelligence development DIY and preparation method thereof |
| CN109575315A (en) * | 2017-09-29 | 2019-04-05 | 中国科学院大学 | A kind of PVA supramolecular hydrogel and the preparation method and application thereof |
| CN110997781A (en) * | 2017-08-15 | 2020-04-10 | 桑福德有限合伙人公司 | Glue Schlemm activator and related methods and kits |
-
2021
- 2021-08-31 CN CN202111010406.4A patent/CN113583370A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694319A (en) * | 2016-01-18 | 2016-06-22 | 袁暾 | Medical polyvinyl alcohol gel and preparing method thereof |
| CN110997781A (en) * | 2017-08-15 | 2020-04-10 | 桑福德有限合伙人公司 | Glue Schlemm activator and related methods and kits |
| CN109575315A (en) * | 2017-09-29 | 2019-04-05 | 中国科学院大学 | A kind of PVA supramolecular hydrogel and the preparation method and application thereof |
| CN108948615A (en) * | 2018-08-28 | 2018-12-07 | 宁波百仕高联合工业有限公司 | A kind of nontoxic crystal mud of intelligence development DIY and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 陈泠颖: "基于动态硼酸酯键交联的敏感性水凝胶制备及其性质研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 陈泠颖: "基于动态硼酸酯键交联的敏感性水凝胶制备及其性质研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 1, 15 January 2021 (2021-01-15), pages 014 - 1300 * |
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