WO2022205702A1 - Heat-sealing-type acrylic emulsion for paper and preparation method therefor - Google Patents

Heat-sealing-type acrylic emulsion for paper and preparation method therefor Download PDF

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Publication number
WO2022205702A1
WO2022205702A1 PCT/CN2021/108884 CN2021108884W WO2022205702A1 WO 2022205702 A1 WO2022205702 A1 WO 2022205702A1 CN 2021108884 W CN2021108884 W CN 2021108884W WO 2022205702 A1 WO2022205702 A1 WO 2022205702A1
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Prior art keywords
monomer
paper
heat
acrylic emulsion
emulsion
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PCT/CN2021/108884
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French (fr)
Chinese (zh)
Inventor
朱清梅
袁业兴
陈穆伟
陈鹏
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海南必凯水性新材料有限公司
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Publication of WO2022205702A1 publication Critical patent/WO2022205702A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the invention relates to the technical field of polymer materials, and more particularly, to a heat-sealing acrylic emulsion for paper and a preparation method thereof.
  • Plastic bags are consumables in daily life, and China consumes a lot of plastic bags every year. While it provides convenience for consumers, it also causes serious waste of resources and environmental pollution due to excessive use and inadequate recycling. In particular, ultra-thin plastic shopping bags are easily damaged, and most of them are discarded at will, becoming the main source of "white pollution”. More and more countries and regions have restricted the production, sale and use of plastic shopping bags.
  • Paper materials have the characteristics of environmental protection, recycling and cost saving. With the increasing environmental protection requirements of packaging materials, paper packaging materials will become the preferred packaging materials in the future. However, the main component of paper is plant fibers, and to make bags, it is necessary to improve the heat sealing performance of the paper surface. In order to solve this problem, the commonly used structure is paper-plastic composite.
  • Chinese Patent Publication No. CN101871187A discloses a paper-plastic composite film, the method is to compound polyethylene film with sealing performance on the other side of the paper, and use the side of the polyethylene film as the inner layer of the bag; After the composite polyethylene film, it is very difficult to recycle and separate the PE layer and then make pulp. If it is allowed to decompose naturally, it will take a long time, causing great pollution to the environment and wasting paper resources.
  • the Chinese Patent Publication No. CN103774490A discloses a preparation method of polylactic acid-coated plastic paper, which is characterized by Degradable polylactic acid particles are used as coating pigments, water-soluble resin, water, dispersant, defoamer and mold release agent are added to prepare a coating, which is coated on the surface of the paper to improve the heat-sealing effect of the paper; but Polylactic acid is produced with organic acid lactic acid as raw material, and its cost is very expensive, which limits the large-scale promotion of this application to a large extent.
  • the purpose of the present invention is to provide a heat-sealable acrylic emulsion for paper and a preparation method thereof.
  • the heat-sealable acrylic emulsion for paper provided by the present invention has high stability, and further obtained coating Excellent heat sealing performance.
  • the invention provides a heat-sealing acrylic emulsion for paper, which is prepared from the raw materials comprising the following components:
  • Emulsifier 0.3 ⁇ 0.6wt%
  • the functional monomer is vinylsulfonic acid and/or acrylamide
  • the cross-linking agent is aziridine and/or imidazole.
  • the degree of polymerization of the PVOH masterbatch is 400-1900, and the degree of alcoholysis is 88%-99%.
  • the hard monomer is selected from one or more of methyl methacrylate, ethyl methacrylate and styrene.
  • the soft monomer is selected from one or more of ethyl acrylate, lauryl methacrylate and n-octyl methacrylate.
  • the emulsifier is sodium lauryl sulfate.
  • the initiator is tert-butyl hydroperoxide.
  • the present invention also provides a method for preparing the heat-sealing acrylic emulsion for paper according to the above technical solution, comprising the following steps:
  • the pre-emulsification process in step a) is carried out under stirring; the stirring speed of the pre-emulsification is 100r/min ⁇ 150r/min, and the time is 0.5h ⁇ 1h;
  • the first amount of water accounts for 8-20 wt % of the total amount of water.
  • the second amount of the pre-emulsified monomer in step b) accounts for 8 to 12 wt % of the total amount of the pre-emulsified monomer
  • the third amount of the initiator solution accounts for 2-4 wt % of the total amount of the initiator solution.
  • the temperature of the seed reaction in step b) is 80°C to 90°C
  • the stirring speed is 80r/min to 130r/min
  • the time is 1h to 2h;
  • the temperature is maintained at 80°C to 90°C;
  • the temperature of the polymerization reaction is 80°C ⁇ 90°C, the stirring speed is 80r/min ⁇ 130r/min, and the time is 1h ⁇ 2h;
  • the stirring speed of the cross-linking reaction is 80r/min ⁇ 130r/min, and the time is 0.5h ⁇ 1h.
  • the invention provides a heat-sealing acrylic emulsion for paper, which is prepared from raw materials including the following components: PVOH master batch 2-5wt%; hard monomer 7-12wt%; soft monomer 5-9wt%; function 0.3-0.6wt% of emulsifier; 0.2-0.5wt% of initiator; 0.3-0.5wt% of cross-linking agent; 0.05-0.1wt% of defoamer; the balance of water; the function
  • the monomers are vinylsulfonic acid and/or acrylamide; the crosslinking agent is aziridine and/or imidazole.
  • the viscosity of the emulsion is enhanced, and a network-like and dense cross-linking structure occurs with the long fibers of the paper, which improves the surface activity of the coating and enhances the adhesion between the coating and the paper;
  • the ratio of each monomer is adjusted to adjust the glass transition temperature of the emulsion.
  • the added cross-linking agent is cross-linked with the carboxyl group in the acrylic emulsion again, which can form a heat-activated acrylic coating and further improve the emulsion.
  • the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
  • the invention provides a heat-sealing acrylic emulsion for paper, which is prepared from the raw materials comprising the following components:
  • Emulsifier 0.3 ⁇ 0.6wt%
  • the functional monomer is vinylsulfonic acid and/or acrylamide
  • the cross-linking agent is aziridine and/or imidazole.
  • the heat-sealing acrylic emulsion for paper is composed of PVOH masterbatch, hard monomer, soft monomer, functional monomer, emulsifier, initiator, cross-linking agent, defoamer and water. It is prepared from raw materials, preferably from PVOH masterbatch, hard monomers, soft monomers, functional monomers, emulsifiers, initiators, crosslinking agents, antifoaming agents and water.
  • the polymerization degree of the PVOH (polyvinyl alcohol) masterbatch is preferably 400-1900, and the alcoholysis degree is preferably 88%-99%.
  • the source of the PVOH masterbatch there is no special restriction on the source of the PVOH masterbatch, and commercially available products well known to those skilled in the art can be used.
  • the hard monomer is preferably one or more selected from methyl methacrylate, ethyl methacrylate and styrene, more preferably methyl methacrylate, ethyl methacrylate or Styrene.
  • the source of the hard monomer is not particularly limited in the present invention, and the commercially available products of the above-mentioned methyl methacrylate, ethyl methacrylate and styrene well known to those skilled in the art can be used.
  • the soft monomer is preferably selected from one or more of ethyl acrylate, lauryl methacrylate and n-octyl methacrylate, more preferably ethyl acrylate, lauryl methacrylate or n-Octyl methacrylate.
  • the source of the soft monomer is not particularly limited in the present invention, and the commercially available products of the above-mentioned ethyl acrylate, lauryl methacrylate and n-octyl methacrylate well known to those skilled in the art can be used.
  • the functional monomer is vinylsulfonic acid and/or acrylamide, preferably vinylsulfonic acid or acrylamide.
  • the source of the functional monomer is not particularly limited in the present invention, and the commercially available products of the above-mentioned vinylsulfonic acid and acrylamide well known to those skilled in the art can be used.
  • the emulsifier is preferably sodium lauryl sulfate; the initiator is preferably tert-butyl hydroperoxide; the cross-linking agent is aziridine and/or imidazole, preferably aziridine or imidazole; the defoamer is preferably a silicone defoamer.
  • the present invention has no special restrictions on the sources of the emulsifier, initiator, crosslinking agent and defoaming agent, and commercial products well known to those skilled in the art can be used.
  • the water is not particularly limited in the present invention, and soft water well known to those skilled in the art can be used.
  • the invention adopts the raw materials of specific content components to prepare the acrylic emulsion, and realizes the overall better interaction.
  • the viscosity of the emulsion is enhanced, and a network-like and dense cross-linking structure occurs with the long fibers of the paper, which improves the surface activity of the coating and enhances the adhesion between the coating and the paper.
  • the glass transition temperature of the emulsion is adjusted.
  • the added cross-linking agent is cross-linked with the carboxyl groups in the acrylic emulsion again, which can form a heat-activated acrylic coating, which further improves the stability of the emulsion and improves the stability of the emulsion after drying. Heat sealing properties of the coating.
  • the present invention also provides a method for preparing the heat-sealing acrylic emulsion for paper according to the above technical solution, comprising the following steps:
  • the hard monomer, the soft monomer, the functional monomer and the emulsifier are firstly mixed and pre-emulsified to obtain the pre-emulsified monomer; the first amount of water and the initiator are mixed to obtain the initiator solution.
  • the hard monomer, soft monomer, functional monomer, emulsifier, water and initiator are the same as those in the above-mentioned technical solutions, and will not be repeated here.
  • the pre-emulsification process is preferably carried out under stirring; the stirring speed of the pre-emulsification is preferably 100r/min ⁇ 150r/min, and the time is preferably 0.5h ⁇ 1h.
  • the first amount of water preferably accounts for 8-20 wt % of the total amount of water, more preferably 13-15 wt %.
  • the second dosage of the pre-emulsified monomer and the third dosage of the initiator solution are added to carry out the seed reaction; and the remaining pre-emulsified monomer is continuously added simultaneously through the metering pump body and initiator solution, the dropping time is controlled to 6h ⁇ 8h; after the addition of materials is completed, the polymerization reaction is carried out, then the temperature is lowered to 70 °C ⁇ 75 °C, the cross-linking agent is added to carry out the cross-linking reaction, and finally the defoaming agent is added to fully stir, After standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
  • the PVOH masterbatch, the crosslinking agent and the defoaming agent are the same as those in the above-mentioned technical solutions, and will not be repeated here.
  • step b) the process of step b) is preferably carried out in a reaction kettle, and the stirring and heating device is turned on.
  • the process of dissolving the PVOH masterbatch with the remaining water is carried out under stirring conditions, the stirring speed is preferably 80r/min ⁇ 130r/min, the temperature is preferably 80°C ⁇ 90°C, and the time is preferably For 1h ⁇ 2h.
  • the second amount of the pre-emulsified monomer preferably accounts for 8-12 wt % of the total amount of the pre-emulsified monomer, more preferably 10 wt %;
  • the third amount of the initiator solution preferably accounts for the total amount of the initiator solution. 2 to 4 wt% of the amount.
  • the temperature of the seed reaction is preferably 80°C to 90°C
  • the stirring speed is preferably 80r/min to 130r/min
  • the time is preferably 1h to 2h.
  • the pre-emulsified monomer and the initiator solution are added dropwise separately, and they are not mixed before adding to the reaction system. .
  • the temperature during the process of adding the remaining pre-emulsified monomer and initiator solution is preferably 80°C to 90°C, which is specifically the same as the temperature of the above-mentioned seed reaction.
  • the temperature of the polymerization reaction is preferably 80°C ⁇ 90°C, and the stirring speed is preferably 80r/min ⁇ 130r/min, which is the same as the temperature and stirring speed of the above-mentioned seed reaction; the time of the polymerization reaction is preferably For 1h ⁇ 2h.
  • the temperature of the cross-linking reaction is the cooling temperature of 70°C to 75°C;
  • the stirring speed of the cross-linking reaction is preferably 80r/min ⁇ 130r/min, which is the same as the stirring speed of the above-mentioned seed reaction;
  • the time of the cross-linking reaction is preferably 0.5 h to 1 h.
  • the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
  • the heat-sealing acrylic emulsion for paper provided by the present invention is coated on base paper of 50g/m 2 to 150g/m 2 and dried with hot air to form coated paper; thus, the heat-sealing acrylic acid for paper can be realized.
  • the dry coating amount of the coated coating is preferably 2 g/m 2 to 5 g/m 2 .
  • the invention provides a heat-sealing acrylic emulsion for paper, which is prepared from raw materials including the following components: PVOH master batch 2-5wt%; hard monomer 7-12wt%; soft monomer 5-9wt%; function 0.3-0.6wt% of emulsifier; 0.2-0.5wt% of initiator; 0.3-0.5wt% of cross-linking agent; 0.05-0.1wt% of defoamer; the balance of water; the function
  • the monomers are vinylsulfonic acid and/or acrylamide; the crosslinking agent is aziridine and/or imidazole.
  • the viscosity of the emulsion is enhanced, and a network-like and dense cross-linking structure occurs with the long fibers of the paper, which improves the surface activity of the coating and enhances the adhesion between the coating and the paper;
  • the ratio of each monomer is adjusted to adjust the glass transition temperature of the emulsion.
  • the added cross-linking agent is cross-linked with the carboxyl group in the acrylic emulsion again, which can form a heat-activated acrylic coating and further improve the emulsion.
  • the preparation method provided by the present invention has simple process, mild conditions and easy control, and has broad application prospects.
  • Described hard monomer is styrene
  • Described soft monomer is ethyl acrylate
  • the degree of polymerization of the PVOH masterbatch is 400, and the degree of alcoholysis is 99%;
  • Described functional monomer is acrylamide
  • Described emulsifier is sodium lauryl sulfate
  • Described initiator is tert-butyl hydroperoxide
  • Described crosslinking agent is aziridine
  • the defoamer is an organosilicon defoamer.
  • reaction temperature was kept at 84 °C during the feeding process; after the feeding was completed, the temperature was kept at 84 °C for 1 hour, then cooled to 73 °C, and 0.44 kg of crosslinking agent was added to react. After 0.8 hours of reaction, 0.06 kg of defoaming agent was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
  • the heat-sealing acrylic emulsion for paper provided in Example 1 of the present invention was coated on a base paper of 150 g/m 2 , and the dry coating amount of the coating was 5 g/m 2 . After drying with hot air, a coated paper was obtained. ; The prepared coated paper is detected, and the results are shown in Table 1.
  • Described hard monomer is ethyl methacrylate
  • Described soft monomer is n-octyl methacrylate
  • the degree of polymerization of the PVOH masterbatch is 500, and the degree of alcoholysis is 97%;
  • Described functional monomer is vinylsulfonic acid
  • Described emulsifier is sodium lauryl sulfate
  • Described initiator is tert-butyl hydroperoxide
  • Described cross-linking agent is imidazole
  • the defoamer is an organosilicon defoamer.
  • the reaction temperature was kept at 87 °C during the feeding process; after the feeding was completed, the temperature was kept at 87 °C for 1.5 hours, then the temperature was lowered to 71 °C, and 0.4 kg of crosslinking agent was added to react. After 0.7 hours of reaction, 0.07 kg of defoamer was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
  • the heat-sealing acrylic emulsion for paper provided in Example 2 of the present invention was coated on a base paper of 140 g/m 2 , and the dry coating amount of the coating was 3.5 g/m 2 . After drying with hot air, a coating was obtained. paper; the prepared coated paper was tested, and the results are shown in Table 2.
  • Described hard monomer is methyl methacrylate
  • Described soft monomer is n-octyl methacrylate
  • the degree of polymerization of the PVOH masterbatch is 1000, and the degree of alcoholysis is 95%;
  • Described functional monomer is acrylamide
  • Described emulsifier is sodium lauryl sulfate
  • Described initiator is tert-butyl hydroperoxide
  • Described crosslinking agent is aziridine
  • the defoamer is an organosilicon defoamer.
  • reaction temperature was kept at 85 °C during the feeding process; after the feeding was completed, the temperature was kept at 85 °C for 2 hours, then the temperature was lowered to 72 °C, and 0.3 kg of crosslinking agent was added to react. After 0.6 hours of reaction, 0.05 kg of defoaming agent was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
  • the heat-sealing acrylic emulsion for paper provided in Example 3 of the present invention was coated on a base paper of 50 g/m 2 , and the dry coating amount of the coating was 4.5 g/m 2 . After drying with hot air, a coating was obtained. paper; the prepared coated paper was tested, and the results are shown in Table 3.
  • Described hard monomer is ethyl methacrylate
  • Described soft monomer is lauryl methacrylate
  • the degree of polymerization of the PVOH masterbatch is 1700, and the degree of alcoholysis is 88%;
  • Described functional monomer is acrylamide
  • Described emulsifier is sodium lauryl sulfate
  • Described initiator is tert-butyl hydroperoxide
  • Described cross-linking agent is imidazole
  • the defoamer is an organosilicon defoamer.
  • reaction temperature was kept at 80 °C during the feeding process; after the feeding was completed, the temperature was kept at 80 °C for 1 hour, then cooled to 75 °C, and 0.3 kg of cross-linking agent was added to react. After 0.5 hours of reaction, 0.1 kg of defoaming agent was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
  • the heat-sealing acrylic emulsion for paper provided in Example 4 of the present invention was coated on 100 g/m 2 of base paper, and the dry coating amount of the coating was 2 g/m 2 . After drying with hot air, a coated paper was obtained ; Detect the coated paper made, and the results are shown in Table 4.
  • Described hard monomer is methyl methacrylate
  • Described soft monomer is ethyl acrylate
  • the degree of polymerization of the PVOH masterbatch is 1900, and the degree of alcoholysis is 90%;
  • Described functional monomer is vinylsulfonic acid
  • Described emulsifier is sodium lauryl sulfate
  • Described initiator is tert-butyl hydroperoxide
  • Described crosslinking agent is aziridine
  • the defoamer is an organosilicon defoamer.
  • reaction temperature was kept at 90 °C during the feeding process; after the feeding was completed, the temperature was kept at 90 °C for 2 hours, then cooled to 70 °C, and 0.5 kg of crosslinking agent was added to react. After 1 hour of reaction, 0.08 kg of defoaming agent was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
  • the heat-sealing acrylic emulsion for paper provided in Example 5 of the present invention was coated on a base paper of 90 g/m 2 , and the dry coating amount of the coating was 4 g/m 2 . After drying with hot air, a coated paper was obtained. ; Detect the coated paper made, and the results are shown in Table 5.
  • Adopt the existing acrylic emulsion specifically the product developed in the embodiment 2 of patent CN102321416A
  • the structure is 80g/m 2 base paper//4g/m 2 acrylic emulsion, that is, the above-mentioned acrylic emulsion is coated on 80 g/m 2 of base paper, coated
  • the dry coating weight of the layer was 4 g/m 2 , and after drying with hot air, the coated paper was obtained;
  • the structure is 80g/m 2 base paper//4g/m 2 polylactic acid coating, that is, the above-mentioned polylactic acid coating is coated on 80g/m 2 On the base paper, the dry coating weight of the coating was 4g/m 2 , and after drying with hot air, the coated paper was obtained;
  • the coated paper prepared by applying the acrylic emulsion of the present invention has excellent heat-sealing performance, and the preparation method provided by the present invention has simple process and low cost, and is very suitable for industrial production.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

Provided is a heat-sealing-type acrylic emulsion for paper. The emulsion is prepared from the following raw materials in percentages by weight: 2-5 wt% of a PVOH master batch, 7-12 wt% of a hard monomer, 5-9 wt% of a soft monomer, 1-3 wt% of a functional monomer, 0.3-0.6 wt% of an emulsifier, 0.2-0.5 wt% of an initiator, 0.3-0.5 wt% of a cross-linking agent, and 0.05-0.1 wt% of a defoaming agent, with the balance being water, wherein the functional monomer is vinyl sulfonic acid and/or acrylamide; and the cross-linking agent is aziridine and/or imidazole. Compared with the prior art, by preparing an acrylic emulsion from raw materials with specific contents of components, the present invention achieves an overall better interaction. On the one hand, the viscosity of the emulsion is enhanced, a reticular compact cross-linked structure is formed with long-strip fibers of paper, the surface activity of a coating is improved, and the bonding force between the coating and the paper is enhanced; on the other hand, the glass transition temperature of the emulsion is adjusted, and after the monomers are completely reacted, the addition of the cross-linking agent for further cross-linking with carboxyl in the acrylic emulsion again can result in the formation of a thermally activated acrylic coating, such that the stability of the emulsion and the heat sealing performance of the coating after drying are further improved.

Description

一种纸张用的热封型丙烯酸乳液及其制备方法A kind of heat-sealing acrylic emulsion for paper and preparation method thereof
本申请要求于2021年3月31日提交中国专利局、申请号为202110347846.2、发明名称为“一种纸张用的热封型丙烯酸乳液及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on March 31, 2021 with the application number 202110347846.2 and the invention titled "A heat-sealing acrylic emulsion for paper and its preparation method", the entire contents of which are Incorporated herein by reference.
技术领域technical field
本发明涉及高分子材料技术领域，更具体地说，是涉及一种纸张用的热封型丙烯酸乳液及其制备方法。The invention relates to the technical field of polymer materials, and more particularly, to a heat-sealing acrylic emulsion for paper and a preparation method thereof.
背景技术Background technique
塑料袋是日常生活中的易耗品，中国每年都要消耗大量的塑料袋。它在为消费者提供便利的同时，由于过量使用及回收处理不到位等原因，也造成了严重的资源浪费和环境污染。特别是超薄塑料购物袋容易破损，大多被随意丢弃，成为“白色污染”的主要来源。越来越多的国家和地区已经限制塑料购物袋的生产、销售、使用。Plastic bags are consumables in daily life, and China consumes a lot of plastic bags every year. While it provides convenience for consumers, it also causes serious waste of resources and environmental pollution due to excessive use and inadequate recycling. In particular, ultra-thin plastic shopping bags are easily damaged, and most of them are discarded at will, becoming the main source of "white pollution". More and more countries and regions have restricted the production, sale and use of plastic shopping bags.
纸张材料具有环保、再循环使用、节约成本等特点，随着国家对包装物环保性要求的日益提高，纸类包装材料今后必将成为首选包装材料。但是纸张的主要成份是植物纤维，要做成袋子需要提升纸张表面的热封性能。为了解决这个问题，目前普遍使用的结构是纸塑复合。如公开号为CN101871187A中国专利公开了一种纸塑复合膜，其方法是在纸张的另一面复合具有执封性能的聚乙烯薄膜，通过聚乙烯膜的那一面做为袋子内层；但是当纸张经过复合聚乙烯薄膜后，若想回收分离PE层后再制成纸浆，难度非常大，若任由自然分解，需要很长的时间，给环境造成了很大污染，同时也浪费了纸资源。Paper materials have the characteristics of environmental protection, recycling and cost saving. With the increasing environmental protection requirements of packaging materials, paper packaging materials will become the preferred packaging materials in the future. However, the main component of paper is plant fibers, and to make bags, it is necessary to improve the heat sealing performance of the paper surface. In order to solve this problem, the commonly used structure is paper-plastic composite. For example, Chinese Patent Publication No. CN101871187A discloses a paper-plastic composite film, the method is to compound polyethylene film with sealing performance on the other side of the paper, and use the side of the polyethylene film as the inner layer of the bag; After the composite polyethylene film, it is very difficult to recycle and separate the PE layer and then make pulp. If it is allowed to decompose naturally, it will take a long time, causing great pollution to the environment and wasting paper resources.
为了杜决纸塑复合材料回收难问题，国内外已经开始研究通过功能涂层来解决纸张的性能，如公开号为CN103774490A的中国专利公开了一种聚乳酸涂塑纸的制备方法，其特点是以可降解的聚乳酸颗粒作为涂布颜料，加入水溶性树脂、水、分散剂、消泡剂及脱模剂，配制成涂料，涂布在纸张表面上，达到提高纸张的热封效果；但是聚乳酸是以有机酸乳酸为原料生产，本身成本非常昂贵，很大程度上限制此应用的大量推广。In order to solve the problem of difficult recycling of paper-plastic composite materials, researches at home and abroad have begun to solve the performance of paper through functional coatings. For example, the Chinese Patent Publication No. CN103774490A discloses a preparation method of polylactic acid-coated plastic paper, which is characterized by Degradable polylactic acid particles are used as coating pigments, water-soluble resin, water, dispersant, defoamer and mold release agent are added to prepare a coating, which is coated on the surface of the paper to improve the heat-sealing effect of the paper; but Polylactic acid is produced with organic acid lactic acid as raw material, and its cost is very expensive, which limits the large-scale promotion of this application to a large extent.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明的目的在于提供一种纸张用的热封型丙烯酸乳液及其制备方法，本发明提供的纸张用的热封型丙烯酸乳液具有较高的稳定性，且进一步得到的涂层热封性能优异。In view of this, the purpose of the present invention is to provide a heat-sealable acrylic emulsion for paper and a preparation method thereof. The heat-sealable acrylic emulsion for paper provided by the present invention has high stability, and further obtained coating Excellent heat sealing performance.
本发明提供了一种纸张用的热封型丙烯酸乳液，由包括以下组分的原料制得：The invention provides a heat-sealing acrylic emulsion for paper, which is prepared from the raw materials comprising the following components:
PVOH母料2～5wt％；PVOH masterbatch 2～5wt%;
硬单体7～12wt％；Hard monomer 7～12wt%;
软单体5～9wt％；Soft monomer 5～9wt%;
功能性单体1～3wt％；Functional monomer 1～3wt%;
乳化剂0.3～0.6wt％；Emulsifier 0.3～0.6wt%;
引发剂0.2～0.5wt％；Initiator 0.2～0.5wt%;
交联剂0.3～0.5wt％；Crosslinking agent 0.3～0.5wt%;
消泡剂0.05～0.1wt％；Defoamer 0.05～0.1wt%;
余量的水；surplus water;
所述功能性单体为乙烯基磺酸和/或丙烯酰胺；The functional monomer is vinylsulfonic acid and/or acrylamide;
所述交联剂为氮丙啶和/或咪唑。The cross-linking agent is aziridine and/or imidazole.
优选的，所述PVOH母料的聚合度为400～1900，醇解度为88％～99％。Preferably, the degree of polymerization of the PVOH masterbatch is 400-1900, and the degree of alcoholysis is 88%-99%.
优选的，所述硬单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯和苯乙烯中的一种或多种。Preferably, the hard monomer is selected from one or more of methyl methacrylate, ethyl methacrylate and styrene.
优选的，所述软单体选自丙烯酸乙酯、甲基丙烯酸月桂酯和甲基丙烯酸正辛酯中的一种或多种。Preferably, the soft monomer is selected from one or more of ethyl acrylate, lauryl methacrylate and n-octyl methacrylate.
优选的，所述乳化剂为十二烷基硫酸钠。Preferably, the emulsifier is sodium lauryl sulfate.
优选的，所述引发剂为叔丁基过氧化氢。Preferably, the initiator is tert-butyl hydroperoxide.
本发明还提供了一种上述技术方案所述的纸张用的热封型丙烯酸乳液的制备方法，包括以下步骤：The present invention also provides a method for preparing the heat-sealing acrylic emulsion for paper according to the above technical solution, comprising the following steps:
a)将硬单体、软单体、功能性单体、乳化剂混合，进行预乳化，得到预乳化单体；a) mixing hard monomer, soft monomer, functional monomer and emulsifier, and pre-emulsification to obtain pre-emulsified monomer;
将第一用量的水和引发剂混合，得到引发剂溶液；Mix the first amount of water with an initiator to obtain an initiator solution;
b)将PVOH母料用剩余的水溶解后，加入第二用量的预乳化单体和第三用量的引发剂溶液，进行种子反应；再通过计量泵同时连续性加入剩余的预乳化单体和引发剂溶液，滴加时间控制为6h～8h；待加料完成后，进行聚合反应，然后降温至70℃～75℃，加入交联剂进行交联反应，最后加入消泡剂充分搅拌，静置待冷却后得到纸张用的热封型丙烯酸乳液。b) after dissolving the PVOH master batch with the remaining water, add the second amount of pre-emulsion monomer and the third amount of initiator solution to carry out the seed reaction; then continuously add the remaining pre-emulsion monomer and Initiator solution, the dropping time is controlled to be 6h ~ 8h; after the addition of materials is completed, the polymerization reaction is carried out, then the temperature is lowered to 70 ° C ~ 75 ° C, the cross-linking agent is added to carry out the cross-linking reaction, and finally the defoaming agent is added. Stir well, let stand After cooling, a heat-sealing acrylic emulsion for paper is obtained.
优选的，步骤a)中所述预乳化的过程在搅拌下进行；所述预乳化的搅拌速度为100r/min～150r/min，时间为0.5h～1h；Preferably, the pre-emulsification process in step a) is carried out under stirring; the stirring speed of the pre-emulsification is 100r/min～150r/min, and the time is 0.5h～1h;
所述第一用量的水占水总量的8～20wt％。The first amount of water accounts for 8-20 wt % of the total amount of water.
优选的，步骤b)中所述第二用量的预乳化单体占预乳化单体总量的8～12wt％；Preferably, the second amount of the pre-emulsified monomer in step b) accounts for 8 to 12 wt % of the total amount of the pre-emulsified monomer;
所述第三用量的引发剂溶液占引发剂溶液总量的2～4wt％。The third amount of the initiator solution accounts for 2-4 wt % of the total amount of the initiator solution.
优选的，步骤b)中所述种子反应的温度为80℃～90℃，搅拌速度为80r/min～130r/min，时间为1h～2h；Preferably, the temperature of the seed reaction in step b) is 80°C to 90°C, the stirring speed is 80r/min to 130r/min, and the time is 1h to 2h;
所述加入剩余的预乳化单体和引发剂溶液的过程保持温度为80℃～90℃；During the process of adding the remaining pre-emulsified monomer and initiator solution, the temperature is maintained at 80°C to 90°C;
所述聚合反应的温度为80℃～90℃，搅拌速度为80r/min～130r/min，时间为1h～2h；The temperature of the polymerization reaction is 80℃～90℃, the stirring speed is 80r/min～130r/min, and the time is 1h～2h;
所述交联反应的搅拌速度为80r/min～130r/min，时间为0.5h～1h。The stirring speed of the cross-linking reaction is 80r/min～130r/min, and the time is 0.5h～1h.
本发明提供了一种纸张用的热封型丙烯酸乳液，由包括以下组分的原料制得：PVOH母料2～5wt％；硬单体7～12wt％；软单体5～9wt％；功能性单体1～3wt％；乳化剂0.3～0.6wt％；引发剂0.2～0.5wt％；交联剂0.3～0.5wt％；消泡剂0.05～0.1wt％；余量的水；所述功能性单体为乙烯基磺酸和/或丙烯酰胺；所述交联剂为氮丙啶和/或咪唑。与现有技术相比，本发明采用特定含量组分的原料制备丙烯酸乳液，实现整体较好的相互作用，加入PVOH母料进行种子反应后，丙烯酸功能性单体中的C＝C官能团嫁接在PVOH的羟基支链上，增强了乳液的粘稠度，和纸张的长条纤维发生网状致密的交联结构，提高涂层的表面活性，增强涂层跟纸张的粘接力；同时通过适合的各单体配比，调节了乳液的玻璃化温度，单体反应完全后，加入的交联剂再次跟丙烯酸乳液中的羧基发生交联，能够形成热活化的丙烯酸涂层，进一步提高了乳液的稳定性及烘干后涂层的热封性能。The invention provides a heat-sealing acrylic emulsion for paper, which is prepared from raw materials including the following components: PVOH master batch 2-5wt%; hard monomer 7-12wt%; soft monomer 5-9wt%; function 0.3-0.6wt% of emulsifier; 0.2-0.5wt% of initiator; 0.3-0.5wt% of cross-linking agent; 0.05-0.1wt% of defoamer; the balance of water; the function The monomers are vinylsulfonic acid and/or acrylamide; the crosslinking agent is aziridine and/or imidazole. Compared with the prior art, the present invention adopts the raw materials of specific content components to prepare the acrylic emulsion, so as to realize the overall better interaction, and after adding the PVOH masterbatch to carry out the seed reaction, the C=C functional group in the acrylic functional monomer is grafted on the acrylic functional monomer. On the hydroxyl branch of PVOH, the viscosity of the emulsion is enhanced, and a network-like and dense cross-linking structure occurs with the long fibers of the paper, which improves the surface activity of the coating and enhances the adhesion between the coating and the paper; The ratio of each monomer is adjusted to adjust the glass transition temperature of the emulsion. After the monomer reacts completely, the added cross-linking agent is cross-linked with the carboxyl group in the acrylic emulsion again, which can form a heat-activated acrylic coating and further improve the emulsion. The stability of the coating and the heat sealing performance of the coating after drying.
另外，本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应用前景。In addition, the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
本发明提供了一种纸张用的热封型丙烯酸乳液，由包括以下组分的原料制得：The invention provides a heat-sealing acrylic emulsion for paper, which is prepared from the raw materials comprising the following components:
PVOH母料2～5wt％；PVOH masterbatch 2～5wt%;
硬单体7～12wt％；Hard monomer 7～12wt%;
软单体5～9wt％；Soft monomer 5～9wt%;
功能性单体1～3wt％；Functional monomer 1～3wt%;
乳化剂0.3～0.6wt％；Emulsifier 0.3～0.6wt%;
引发剂0.2～0.5wt％；Initiator 0.2～0.5wt%;
交联剂0.3～0.5wt％；Crosslinking agent 0.3～0.5wt%;
消泡剂0.05～0.1wt％；Defoamer 0.05～0.1wt%;
余量的水；surplus water;
所述功能性单体为乙烯基磺酸和/或丙烯酰胺；The functional monomer is vinylsulfonic acid and/or acrylamide;
所述交联剂为氮丙啶和/或咪唑。The cross-linking agent is aziridine and/or imidazole.
在本发明中，所述纸张用的热封型丙烯酸乳液由包括PVOH母料、硬单体、软单体、功能性单体、乳化剂、引发剂、交联剂、消泡剂和水的原料制得，优选由PVOH母料、硬单体、软单体、功能性单体、乳化剂、引发剂、交联剂、消泡剂和水制得。In the present invention, the heat-sealing acrylic emulsion for paper is composed of PVOH masterbatch, hard monomer, soft monomer, functional monomer, emulsifier, initiator, cross-linking agent, defoamer and water. It is prepared from raw materials, preferably from PVOH masterbatch, hard monomers, soft monomers, functional monomers, emulsifiers, initiators, crosslinking agents, antifoaming agents and water.
在本发明中，所述PVOH(聚乙烯醇)母料的聚合度优选为400～1900，醇解度优选为88％～99％。本发明对所述PVOH母料的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。In the present invention, the polymerization degree of the PVOH (polyvinyl alcohol) masterbatch is preferably 400-1900, and the alcoholysis degree is preferably 88%-99%. In the present invention, there is no special restriction on the source of the PVOH masterbatch, and commercially available products well known to those skilled in the art can be used.
在本发明中，所述硬单体优选选自甲基丙烯酸甲酯、甲基丙烯酸乙酯和苯 乙烯中的一种或多种，更优选为甲基丙烯酸甲酯、甲基丙烯酸乙酯或苯乙烯。本发明对所述硬单体的来源没有特殊限制，采用本领域技术人员熟知的上述甲基丙烯酸甲酯、甲基丙烯酸乙酯和苯乙烯的市售商品即可。In the present invention, the hard monomer is preferably one or more selected from methyl methacrylate, ethyl methacrylate and styrene, more preferably methyl methacrylate, ethyl methacrylate or Styrene. The source of the hard monomer is not particularly limited in the present invention, and the commercially available products of the above-mentioned methyl methacrylate, ethyl methacrylate and styrene well known to those skilled in the art can be used.
在本发明中，所述软单体优选选自丙烯酸乙酯、甲基丙烯酸月桂酯和甲基丙烯酸正辛酯中的一种或多种，更优选为丙烯酸乙酯、甲基丙烯酸月桂酯或甲基丙烯酸正辛酯。本发明对所述软单体的来源没有特殊限制，采用本领域技术人员熟知的上述丙烯酸乙酯、甲基丙烯酸月桂酯和甲基丙烯酸正辛酯的市售商品即可。In the present invention, the soft monomer is preferably selected from one or more of ethyl acrylate, lauryl methacrylate and n-octyl methacrylate, more preferably ethyl acrylate, lauryl methacrylate or n-Octyl methacrylate. The source of the soft monomer is not particularly limited in the present invention, and the commercially available products of the above-mentioned ethyl acrylate, lauryl methacrylate and n-octyl methacrylate well known to those skilled in the art can be used.
在本发明中，所述功能性单体为乙烯基磺酸和/或丙烯酰胺，优选为乙烯基磺酸或丙烯酰胺。本发明对所述功能性单体的来源没有特殊限制，采用本领域技术人员熟知的上述乙烯基磺酸和丙烯酰胺的市售商品即可。In the present invention, the functional monomer is vinylsulfonic acid and/or acrylamide, preferably vinylsulfonic acid or acrylamide. The source of the functional monomer is not particularly limited in the present invention, and the commercially available products of the above-mentioned vinylsulfonic acid and acrylamide well known to those skilled in the art can be used.
在本发明中，所述乳化剂优选为十二烷基硫酸钠；所述引发剂优选为叔丁基过氧化氢；所述交联剂为氮丙啶和/或咪唑，优选为氮丙啶或咪唑；所述消泡剂优选为有机硅消泡剂。本发明对所述乳化剂、引发剂、交联剂和消泡剂的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。In the present invention, the emulsifier is preferably sodium lauryl sulfate; the initiator is preferably tert-butyl hydroperoxide; the cross-linking agent is aziridine and/or imidazole, preferably aziridine or imidazole; the defoamer is preferably a silicone defoamer. The present invention has no special restrictions on the sources of the emulsifier, initiator, crosslinking agent and defoaming agent, and commercial products well known to those skilled in the art can be used.
本发明对所述水没有特殊限制，采用本领域技术人员熟知的软水即可。The water is not particularly limited in the present invention, and soft water well known to those skilled in the art can be used.
本发明采用特定含量组分的原料制备丙烯酸乳液，实现整体较好的相互作用，加入PVOH母料进行种子反应后，丙烯酸功能性单体中的C＝C官能团嫁接在PVOH的羟基支链上，增强了乳液的粘稠度，和纸张的长条纤维发生网状致密的交联结构，提高涂层的表面活性，增强涂层跟纸张的粘接力；同时通过适合的各单体配比，调节了乳液的玻璃化温度，单体反应完全后，加入的交联剂再次跟丙烯酸乳液中的羧基发生交联，能够形成热活化的丙烯酸涂层，进一步提高了乳液的稳定性及烘干后涂层的热封性能。The invention adopts the raw materials of specific content components to prepare the acrylic emulsion, and realizes the overall better interaction. After adding the PVOH masterbatch to carry out the seed reaction, the C=C functional group in the acrylic functional monomer is grafted on the hydroxyl branch of PVOH, The viscosity of the emulsion is enhanced, and a network-like and dense cross-linking structure occurs with the long fibers of the paper, which improves the surface activity of the coating and enhances the adhesion between the coating and the paper. The glass transition temperature of the emulsion is adjusted. After the monomer reacts completely, the added cross-linking agent is cross-linked with the carboxyl groups in the acrylic emulsion again, which can form a heat-activated acrylic coating, which further improves the stability of the emulsion and improves the stability of the emulsion after drying. Heat sealing properties of the coating.
本发明还提供了一种上述技术方案所述的纸张用的热封型丙烯酸乳液的制备方法，包括以下步骤：The present invention also provides a method for preparing the heat-sealing acrylic emulsion for paper according to the above technical solution, comprising the following steps:
a)将硬单体、软单体、功能性单体、乳化剂混合，进行预乳化，得到预乳化单体；a) mixing hard monomer, soft monomer, functional monomer and emulsifier, and pre-emulsification to obtain pre-emulsified monomer;
将第一用量的水和引发剂混合，得到引发剂溶液；Mix the first amount of water with an initiator to obtain an initiator solution;
b)将PVOH母料用剩余的水溶解后，加入第二用量的预乳化单体和第三 用量的引发剂溶液，进行种子反应；再通过计量泵同时连续性加入剩余的预乳化单体和引发剂溶液，滴加时间控制为6h～8h；待加料完成后，进行聚合反应，然后降温至70℃～75℃，加入交联剂进行交联反应，最后加入消泡剂充分搅拌，静置待冷却后得到纸张用的热封型丙烯酸乳液。b) after dissolving the PVOH master batch with the remaining water, add the second amount of pre-emulsion monomer and the third amount of initiator solution to carry out the seed reaction; then continuously add the remaining pre-emulsion monomer and Initiator solution, the dropping time is controlled to be 6h ~ 8h; after the addition of materials is completed, the polymerization reaction is carried out, then the temperature is lowered to 70 ° C ~ 75 ° C, the cross-linking agent is added to carry out the cross-linking reaction, and finally the defoaming agent is added. Stir well, let stand After cooling, a heat-sealing acrylic emulsion for paper is obtained.
本发明首先将硬单体、软单体、功能性单体、乳化剂混合，进行预乳化，得到预乳化单体；将第一用量的水和引发剂混合，得到引发剂溶液。In the present invention, the hard monomer, the soft monomer, the functional monomer and the emulsifier are firstly mixed and pre-emulsified to obtain the pre-emulsified monomer; the first amount of water and the initiator are mixed to obtain the initiator solution.
在本发明中，所述硬单体、软单体、功能性单体、乳化剂、水和引发剂与上述技术方案中的相同，在此不再赘述。In the present invention, the hard monomer, soft monomer, functional monomer, emulsifier, water and initiator are the same as those in the above-mentioned technical solutions, and will not be repeated here.
在本发明中，所述预乳化的过程优选在搅拌下进行；所述预乳化的搅拌速度优选为100r/min～150r/min，时间优选为0.5h～1h。In the present invention, the pre-emulsification process is preferably carried out under stirring; the stirring speed of the pre-emulsification is preferably 100r/min～150r/min, and the time is preferably 0.5h～1h.
在本发明中，所述第一用量的水优选占水总量的8～20wt％，更优选为13～15wt％。In the present invention, the first amount of water preferably accounts for 8-20 wt % of the total amount of water, more preferably 13-15 wt %.
之后，本发明将PVOH母料用剩余的水溶解后，加入第二用量的预乳化单体和第三用量的引发剂溶液，进行种子反应；再通过计量泵同时连续性加入剩余的预乳化单体和引发剂溶液，滴加时间控制为6h～8h；待加料完成后，进行聚合反应，然后降温至70℃～75℃，加入交联剂进行交联反应，最后加入消泡剂充分搅拌，静置待冷却后得到纸张用的热封型丙烯酸乳液。Then, in the present invention, after dissolving the PVOH masterbatch with the remaining water, the second dosage of the pre-emulsified monomer and the third dosage of the initiator solution are added to carry out the seed reaction; and the remaining pre-emulsified monomer is continuously added simultaneously through the metering pump body and initiator solution, the dropping time is controlled to 6h ~ 8h; after the addition of materials is completed, the polymerization reaction is carried out, then the temperature is lowered to 70 ℃ ~ 75 ℃, the cross-linking agent is added to carry out the cross-linking reaction, and finally the defoaming agent is added to fully stir, After standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
在本发明中，所述PVOH母料、交联剂和消泡剂与上述技术方案中的相同，在此不再赘述。In the present invention, the PVOH masterbatch, the crosslinking agent and the defoaming agent are the same as those in the above-mentioned technical solutions, and will not be repeated here.
在本发明中，所述步骤b)的过程优选在反应釜中进行，并开启搅拌和加热装置。In the present invention, the process of step b) is preferably carried out in a reaction kettle, and the stirring and heating device is turned on.
在本发明中，所述将PVOH母料用剩余的水溶解的过程在搅拌条件下进行，所述搅拌的转速优选为80r/min～130r/min，温度优选为80℃～90℃，时间优选为1h～2h。In the present invention, the process of dissolving the PVOH masterbatch with the remaining water is carried out under stirring conditions, the stirring speed is preferably 80r/min～130r/min, the temperature is preferably 80℃～90℃, and the time is preferably For 1h ~ 2h.
在本发明中，所述第二用量的预乳化单体优选占预乳化单体总量的8～12wt％，更优选为10wt％；所述第三用量的引发剂溶液优选占引发剂溶液总量的2～4wt％。In the present invention, the second amount of the pre-emulsified monomer preferably accounts for 8-12 wt % of the total amount of the pre-emulsified monomer, more preferably 10 wt %; the third amount of the initiator solution preferably accounts for the total amount of the initiator solution. 2 to 4 wt% of the amount.
在本发明中，所述种子反应的温度优选为80℃～90℃，搅拌速度优选为80r/min～130r/min，时间优选为1h～2h。In the present invention, the temperature of the seed reaction is preferably 80°C to 90°C, the stirring speed is preferably 80r/min to 130r/min, and the time is preferably 1h to 2h.
在本发明中，所述通过计量泵同时连续性加入剩余的预乳化单体和引发剂溶液的过程中，预乳化单体和引发剂溶液采用分别滴加的方式，加入反应体系前并未混合。In the present invention, in the process of adding the remaining pre-emulsified monomer and initiator solution simultaneously and continuously through the metering pump, the pre-emulsified monomer and the initiator solution are added dropwise separately, and they are not mixed before adding to the reaction system. .
在本发明中，所述加入剩余的预乳化单体和引发剂溶液的过程保持温度优选为80℃～90℃，具体与上述种子反应的温度相同。In the present invention, the temperature during the process of adding the remaining pre-emulsified monomer and initiator solution is preferably 80°C to 90°C, which is specifically the same as the temperature of the above-mentioned seed reaction.
在本发明中，所述聚合反应的温度优选为80℃～90℃，搅拌速度优选为80r/min～130r/min，具体与上述种子反应的温度及搅拌速度相同；所述聚合反应的时间优选为1h～2h。In the present invention, the temperature of the polymerization reaction is preferably 80℃～90℃, and the stirring speed is preferably 80r/min～130r/min, which is the same as the temperature and stirring speed of the above-mentioned seed reaction; the time of the polymerization reaction is preferably For 1h ~ 2h.
在本发明中，所述交联反应的温度即降温的温度70℃～75℃；所述交联反应的搅拌速度优选为80r/min～130r/min，具体与上述种子反应的搅拌速度相同；所述交联反应的时间优选为0.5h～1h。In the present invention, the temperature of the cross-linking reaction is the cooling temperature of 70°C to 75°C; the stirring speed of the cross-linking reaction is preferably 80r/min～130r/min, which is the same as the stirring speed of the above-mentioned seed reaction; The time of the cross-linking reaction is preferably 0.5 h to 1 h.
本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应用前景。The preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
本发明提供的纸张用的热封型丙烯酸乳液通过涂布在50g/m 2～150g/m 2的原纸上，经热风烘干后，制成涂布纸；从而实现纸张用的热封型丙烯酸乳液在制备涂布纸的应用。在本发明中，所述涂布的涂层干涂布量优选为2g/m 2～5g/m 2。 The heat-sealing acrylic emulsion for paper provided by the present invention is coated on base paper of 50g/m 2 to 150g/m 2 and dried with hot air to form coated paper; thus, the heat-sealing acrylic acid for paper can be realized. The application of emulsions in the preparation of coated paper. In the present invention, the dry coating amount of the coated coating is preferably 2 g/m 2 to 5 g/m 2 .
本发明提供了一种纸张用的热封型丙烯酸乳液，由包括以下组分的原料制得：PVOH母料2～5wt％；硬单体7～12wt％；软单体5～9wt％；功能性单体1～3wt％；乳化剂0.3～0.6wt％；引发剂0.2～0.5wt％；交联剂0.3～0.5wt％；消泡剂0.05～0.1wt％；余量的水；所述功能性单体为乙烯基磺酸和/或丙烯酰胺；所述交联剂为氮丙啶和/或咪唑。与现有技术相比，本发明采用特定含量组分的原料制备丙烯酸乳液，实现整体较好的相互作用，加入PVOH母料进行种子反应后，丙烯酸功能性单体中的C＝C官能团嫁接在PVOH的羟基支链上，增强了乳液的粘稠度，和纸张的长条纤维发生网状致密的交联结构，提高涂层的表面活性，增强涂层跟纸张的粘接力；同时通过适合的各单体配比，调节了乳液的玻璃化温度，单体反应完全后，加入的交联剂再次跟丙烯酸乳液中的羧基发生交联，能够形成热活化的丙烯酸涂层，进一步提高了乳液的稳定性及烘干后涂层的热封性能。The invention provides a heat-sealing acrylic emulsion for paper, which is prepared from raw materials including the following components: PVOH master batch 2-5wt%; hard monomer 7-12wt%; soft monomer 5-9wt%; function 0.3-0.6wt% of emulsifier; 0.2-0.5wt% of initiator; 0.3-0.5wt% of cross-linking agent; 0.05-0.1wt% of defoamer; the balance of water; the function The monomers are vinylsulfonic acid and/or acrylamide; the crosslinking agent is aziridine and/or imidazole. Compared with the prior art, the present invention adopts the raw materials of specific content components to prepare the acrylic emulsion, so as to realize the overall better interaction, and after adding the PVOH masterbatch to carry out the seed reaction, the C=C functional group in the acrylic functional monomer is grafted on the acrylic functional monomer. On the hydroxyl branch of PVOH, the viscosity of the emulsion is enhanced, and a network-like and dense cross-linking structure occurs with the long fibers of the paper, which improves the surface activity of the coating and enhances the adhesion between the coating and the paper; The ratio of each monomer is adjusted to adjust the glass transition temperature of the emulsion. After the monomer reacts completely, the added cross-linking agent is cross-linked with the carboxyl group in the acrylic emulsion again, which can form a heat-activated acrylic coating and further improve the emulsion. The stability of the coating and the heat sealing performance of the coating after drying.
另外，本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应 用前景。In addition, the preparation method provided by the present invention has simple process, mild conditions and easy control, and has broad application prospects.
为了进一步说明本发明，下面通过以下实施例进行详细说明。本发明以下实施例所用原料均为市售；热封强度的检测方法为GB/T2358-98。In order to further illustrate the present invention, the following examples are used for detailed description. The raw materials used in the following examples of the present invention are all commercially available; the detection method of heat sealing strength is GB/T2358-98.
实施例1Example 1
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021108884-appb-000001
Figure PCTCN2021108884-appb-000001
所述的硬单体为苯乙烯；Described hard monomer is styrene;
所述的软单体为丙烯酸乙酯；Described soft monomer is ethyl acrylate;
所述的PVOH母料聚合度为400，醇解度为99％；The degree of polymerization of the PVOH masterbatch is 400, and the degree of alcoholysis is 99%;
所述的功能性单体为丙烯酰胺；Described functional monomer is acrylamide;
所述的乳化剂为十二烷基硫酸钠；Described emulsifier is sodium lauryl sulfate;
所述的引发剂为叔丁基过氧化氢；Described initiator is tert-butyl hydroperoxide;
所述的交联剂为氮丙啶；Described crosslinking agent is aziridine;
所述的消泡剂为有机硅消泡剂。The defoamer is an organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
①将12kg的硬单体、9kg的软单体、2.6kg的功能性单体、0.6kg的乳化剂加入到A料罐中，搅拌0.5小时，搅拌速度为150转/min，进行预乳化，得到预乳化单体待用；①Add 12kg of hard monomer, 9kg of soft monomer, 2.6kg of functional monomer, and 0.6kg of emulsifier into the A material tank, stir for 0.5 hours, and carry out pre-emulsification at a stirring speed of 150 rpm. The pre-emulsified monomer is obtained for use;
将10kg的软水和0.3kg引发剂加入到B料罐中，搅拌均匀，配成引发剂溶液，待用。Add 10kg of soft water and 0.3kg of initiator into the B material tank, stir evenly, and prepare an initiator solution, which is ready for use.
②在反应釜中加入剩余的软水，3kg的PVOH母料，开启搅拌和加热装置， 搅拌速度设定为95r/min，加热到84℃后，保温1.6小时，待PVOH母料完全溶解，加入2.42kg的预乳化单体，0.4kg的引发剂溶液，进行种子反应，反应时间1.7小时后，通过计量泵同时连续性加入配制好的预乳化单体和引发剂溶液，滴加时间控制为6小时，加料过程保持反应温度为84℃；待加料完成后，继续保温84℃1小时，然后降温到73℃，加入0.44kg的交联剂进行反应，反应0.8小时后，加入0.06kg的消泡剂充分搅拌，静置待冷却后，得到纸张用的热封型丙烯酸乳液。②Add the remaining soft water and 3kg of PVOH masterbatch into the reaction kettle, turn on the stirring and heating device, set the stirring speed to 95r/min, heat to 84°C, keep the temperature for 1.6 hours, and wait until the PVOH masterbatch is completely dissolved, add 2.42 rpm kg of pre-emulsified monomer, 0.4 kg of initiator solution, and the seed reaction was carried out. After the reaction time was 1.7 hours, the prepared pre-emulsified monomer and initiator solution were simultaneously added continuously through the metering pump, and the dripping time was controlled to 6 hours. , the reaction temperature was kept at 84 °C during the feeding process; after the feeding was completed, the temperature was kept at 84 °C for 1 hour, then cooled to 73 °C, and 0.44 kg of crosslinking agent was added to react. After 0.8 hours of reaction, 0.06 kg of defoaming agent was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
将本发明实施例1提供的纸张用的热封型丙烯酸乳液，涂布在150g/m 2的原纸上，涂层干涂布量为5g/m 2，经热风烘干后，得到涂布纸；将制成的涂布纸进行检测，结果参见表1所示。 The heat-sealing acrylic emulsion for paper provided in Example 1 of the present invention was coated on a base paper of 150 g/m 2 , and the dry coating amount of the coating was 5 g/m 2 . After drying with hot air, a coated paper was obtained. ; The prepared coated paper is detected, and the results are shown in Table 1.
表1 应用本发明实施例1提供的纸张用的热封型丙烯酸乳液的涂布纸各项性能数据Table 1 Various performance data of coated paper using the heat-sealing acrylic emulsion for paper provided in Example 1 of the present invention
Figure PCTCN2021108884-appb-000002
Figure PCTCN2021108884-appb-000002
实施例2Example 2
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021108884-appb-000003
Figure PCTCN2021108884-appb-000003
所述的硬单体为甲基丙烯酸乙酯；Described hard monomer is ethyl methacrylate;
所述的软单体为甲基丙烯酸正辛酯；Described soft monomer is n-octyl methacrylate;
所述的PVOH母料聚合度为500，醇解度为97％；The degree of polymerization of the PVOH masterbatch is 500, and the degree of alcoholysis is 97%;
所述的功能性单体为乙烯基磺酸；Described functional monomer is vinylsulfonic acid;
所述的乳化剂为十二烷基硫酸钠；Described emulsifier is sodium lauryl sulfate;
所述的引发剂为叔丁基过氧化氢；Described initiator is tert-butyl hydroperoxide;
所述的交联剂为咪唑；Described cross-linking agent is imidazole;
所述的消泡剂为有机硅消泡剂。The defoamer is an organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
①将8kg的硬单体、8kg的软单体、2.73kg的功能性单体、0.3kg的乳化剂加入到A料罐中，搅拌1小时，搅拌速度为100转/min，进行预乳化，得到预乳化单体待用；①Add 8kg of hard monomer, 8kg of soft monomer, 2.73kg of functional monomer, and 0.3kg of emulsifier into the A material tank, stir for 1 hour, and the stirring speed is 100 rev/min to carry out pre-emulsification, The pre-emulsified monomer is obtained for use;
将11kg的软水和0.5kg引发剂加入到B料罐中，搅拌均匀，配成引发剂溶液，待用。Add 11kg of soft water and 0.5kg of initiator into the B material tank, stir evenly, and prepare an initiator solution for use.
②在反应釜中加入剩余的软水，5kg的PVOH母料，开启搅拌和加热装置，搅拌速度设定为120r/min，加热到87℃后，保温1小时，待PVOH母料完全溶解，加入1.9kg的预乳化单体，0.34kg的引发剂溶液，进行种子反应，反应时间1.4小时后，通过计量泵同时连续性加入配制好的预乳化单体和引发剂溶液，滴加时间控制为7.5小时，加料过程保持反应温度为87℃；待加料完成后，继续保温87℃1.5小时，然后降温到71℃，加入0.4kg的交联剂进行反应，反应0.7小时后，加入0.07kg的消泡剂充分搅拌，静置待冷却后，得到纸张用的热封型丙烯酸乳液。②Add the remaining soft water and 5kg of PVOH masterbatch into the reaction kettle, turn on the stirring and heating device, set the stirring speed to 120r/min, heat it to 87°C, keep the temperature for 1 hour, and when the PVOH masterbatch is completely dissolved, add 1.9 kg of pre-emulsified monomer, 0.34 kg of initiator solution, and the seed reaction was carried out. After the reaction time was 1.4 hours, the prepared pre-emulsified monomer and initiator solution were continuously added simultaneously through the metering pump, and the dripping time was controlled to 7.5 hours. , the reaction temperature was kept at 87 °C during the feeding process; after the feeding was completed, the temperature was kept at 87 °C for 1.5 hours, then the temperature was lowered to 71 °C, and 0.4 kg of crosslinking agent was added to react. After 0.7 hours of reaction, 0.07 kg of defoamer was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
将本发明实施例2提供的纸张用的热封型丙烯酸乳液，涂布在140g/m 2的原纸上，涂层干涂布量为3.5g/m 2，经热风烘干后，得到涂布纸；将制成的涂布纸进行检测，结果参见表2所示。 The heat-sealing acrylic emulsion for paper provided in Example 2 of the present invention was coated on a base paper of 140 g/m 2 , and the dry coating amount of the coating was 3.5 g/m 2 . After drying with hot air, a coating was obtained. paper; the prepared coated paper was tested, and the results are shown in Table 2.
表2 应用本发明实施例2提供的纸张用的热封型丙烯酸乳液的涂布纸各项性能数据Table 2 Various performance data of coated paper using the heat-sealing acrylic emulsion for paper provided in Example 2 of the present invention
Figure PCTCN2021108884-appb-000004
Figure PCTCN2021108884-appb-000004
实施例3Example 3
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021108884-appb-000005
Figure PCTCN2021108884-appb-000005
所述的硬单体为甲基丙烯酸甲酯；Described hard monomer is methyl methacrylate;
所述的软单体为甲基丙烯酸正辛酯；Described soft monomer is n-octyl methacrylate;
所述的PVOH母料聚合度为1000，醇解度为95％；The degree of polymerization of the PVOH masterbatch is 1000, and the degree of alcoholysis is 95%;
所述的功能性单体为丙烯酰胺；Described functional monomer is acrylamide;
所述的乳化剂为十二烷基硫酸钠；Described emulsifier is sodium lauryl sulfate;
所述的引发剂为叔丁基过氧化氢；Described initiator is tert-butyl hydroperoxide;
所述的交联剂为氮丙啶；Described crosslinking agent is aziridine;
所述的消泡剂为有机硅消泡剂。The defoamer is an organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
①将7kg的硬单体、7kg的软单体、1kg的功能性单体、0.45kg的乳化剂加入到A料罐中，搅拌0.8小时，搅拌速度为120转/min，进行预乳化，得到预乳化单体待用；① Add 7kg of hard monomer, 7kg of soft monomer, 1kg of functional monomer, and 0.45kg of emulsifier into the A material tank, stir for 0.8 hours, and carry out pre-emulsification at a stirring speed of 120 rpm to obtain The pre-emulsified monomer is ready for use;
将12kg的软水和0.2kg引发剂加入到B料罐中，搅拌均匀，配成引发剂溶液，待用。Add 12 kg of soft water and 0.2 kg of initiator into the B material tank, stir evenly, and prepare an initiator solution, which is ready for use.
②在反应釜中加入剩余的软水，2kg的PVOH母料，开启搅拌和加热装置，搅拌速度设定为100r/min，加热到85℃后，保温1小时，待PVOH母料完全溶解，加入1.55kg的预乳化单体，0.36kg的引发剂溶液，进行种子反应，反应时间2小时后，通过计量泵同时连续性加入配制好的预乳化单体和引发剂溶 液，滴加时间控制为7小时，加料过程保持反应温度为85℃；待加料完成后，继续保温85℃2小时，然后降温到72℃，加入0.3kg的交联剂进行反应，反应0.6小时后，加入0.05kg的消泡剂充分搅拌，静置待冷却后，得到纸张用的热封型丙烯酸乳液。②Add the remaining soft water and 2kg of PVOH masterbatch to the reaction kettle, turn on the stirring and heating device, set the stirring speed to 100r/min, heat to 85°C, keep the temperature for 1 hour, and wait until the PVOH masterbatch is completely dissolved, add 1.55 rpm kg of pre-emulsified monomer, 0.36 kg of initiator solution, and the seed reaction was carried out. After the reaction time was 2 hours, the prepared pre-emulsified monomer and initiator solution were simultaneously added continuously through the metering pump, and the dripping time was controlled to 7 hours. , the reaction temperature was kept at 85 °C during the feeding process; after the feeding was completed, the temperature was kept at 85 °C for 2 hours, then the temperature was lowered to 72 °C, and 0.3 kg of crosslinking agent was added to react. After 0.6 hours of reaction, 0.05 kg of defoaming agent was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
将本发明实施例3提供的纸张用的热封型丙烯酸乳液，涂布在50g/m 2的原纸上，涂层干涂布量为4.5g/m 2，经热风烘干后，得到涂布纸；将制成的涂布纸进行检测，结果参见表3所示。 The heat-sealing acrylic emulsion for paper provided in Example 3 of the present invention was coated on a base paper of 50 g/m 2 , and the dry coating amount of the coating was 4.5 g/m 2 . After drying with hot air, a coating was obtained. paper; the prepared coated paper was tested, and the results are shown in Table 3.
表3 应用本发明实施例3提供的纸张用的热封型丙烯酸乳液的涂布纸各项性能数据Table 3 Various performance data of coated paper using the heat-sealing acrylic emulsion for paper provided in Example 3 of the present invention
Figure PCTCN2021108884-appb-000006
Figure PCTCN2021108884-appb-000006
实施例4Example 4
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021108884-appb-000007
Figure PCTCN2021108884-appb-000007
所述的硬单体为甲基丙烯酸乙酯；Described hard monomer is ethyl methacrylate;
所述的软单体为甲基丙烯酸月桂酯；Described soft monomer is lauryl methacrylate;
所述的PVOH母料聚合度为1700，醇解度为88％；The degree of polymerization of the PVOH masterbatch is 1700, and the degree of alcoholysis is 88%;
所述的功能性单体为丙烯酰胺；Described functional monomer is acrylamide;
所述的乳化剂为十二烷基硫酸钠；Described emulsifier is sodium lauryl sulfate;
所述的引发剂为叔丁基过氧化氢；Described initiator is tert-butyl hydroperoxide;
所述的交联剂为咪唑；Described cross-linking agent is imidazole;
所述的消泡剂为有机硅消泡剂。The defoamer is an organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
①将9kg的硬单体、6kg的软单体、1.6kg的功能性单体、0.6kg的乳化剂加入到A料罐中，搅拌0.6小时，搅拌速度为140转/min，进行预乳化，得到预乳化单体待用；①Add 9kg of hard monomer, 6kg of soft monomer, 1.6kg of functional monomer, and 0.6kg of emulsifier to the A material tank, stir for 0.6 hours, and the stirring speed is 140 rpm/min to carry out pre-emulsification, The pre-emulsified monomer is obtained for use;
将11.5kg的软水和0.4kg引发剂加入到B料罐中，搅拌均匀，配成引发剂溶液，待用。Add 11.5kg of soft water and 0.4kg of initiator into the B material tank, stir evenly, and prepare an initiator solution for use.
②在反应釜中加入剩余的软水，4kg的PVOH母料，开启搅拌和加热装置，搅拌速度设定为130r/min，加热到80℃后，保温2小时，待PVOH母料完全溶解，加入1.72kg的预乳化单体，0.37kg的引发剂溶液，进行种子反应，反应时间2小时后，通过计量泵同时连续性加入配制好的预乳化单体和引发剂溶液，滴加时间控制为6.5小时，加料过程保持反应温度为80℃；待加料完成后，继续保温80℃1小时，然后降温到75℃，加入0.3kg的交联剂进行反应，反应0.5小时后，加入0.1kg的消泡剂充分搅拌，静置待冷却后，得到纸张用的热封型丙烯酸乳液。②Add the remaining soft water and 4kg of PVOH masterbatch into the reaction kettle, turn on the stirring and heating device, set the stirring speed to 130r/min, heat to 80°C, keep the temperature for 2 hours, and when the PVOH masterbatch is completely dissolved, add 1.72 rpm kg of pre-emulsified monomer, 0.37 kg of initiator solution, and the seed reaction was carried out. After 2 hours of reaction time, the prepared pre-emulsified monomer and initiator solution were added simultaneously and continuously through the metering pump, and the dripping time was controlled to 6.5 hours. , the reaction temperature was kept at 80 °C during the feeding process; after the feeding was completed, the temperature was kept at 80 °C for 1 hour, then cooled to 75 °C, and 0.3 kg of cross-linking agent was added to react. After 0.5 hours of reaction, 0.1 kg of defoaming agent was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
将本发明实施例4提供的纸张用的热封型丙烯酸乳液，涂布在100g/m 2的原纸上，涂层干涂布量为2g/m 2，经热风烘干后，得到涂布纸；将制成的涂布纸进行检测，结果参见表4所示。 The heat-sealing acrylic emulsion for paper provided in Example 4 of the present invention was coated on 100 g/m 2 of base paper, and the dry coating amount of the coating was 2 g/m 2 . After drying with hot air, a coated paper was obtained ; Detect the coated paper made, and the results are shown in Table 4.
表4 应用本发明实施例4提供的纸张用的热封型丙烯酸乳液的涂布纸各项性能数据Table 4 Various performance data of coated paper using the heat-sealing acrylic emulsion for paper provided in Example 4 of the present invention
Figure PCTCN2021108884-appb-000008
Figure PCTCN2021108884-appb-000008
实施例5Example 5
(1)原料重量配比及具体种类限定：(1) Raw material weight ratio and specific type limitation:
Figure PCTCN2021108884-appb-000009
Figure PCTCN2021108884-appb-000009
Figure PCTCN2021108884-appb-000010
Figure PCTCN2021108884-appb-000010
所述的硬单体为甲基丙烯酸甲酯；Described hard monomer is methyl methacrylate;
所述的软单体为丙烯酸乙酯；Described soft monomer is ethyl acrylate;
所述的PVOH母料聚合度为1900，醇解度为90％；The degree of polymerization of the PVOH masterbatch is 1900, and the degree of alcoholysis is 90%;
所述的功能性单体为乙烯基磺酸；Described functional monomer is vinylsulfonic acid;
所述的乳化剂为十二烷基硫酸钠；Described emulsifier is sodium lauryl sulfate;
所述的引发剂为叔丁基过氧化氢；Described initiator is tert-butyl hydroperoxide;
所述的交联剂为氮丙啶；Described crosslinking agent is aziridine;
所述的消泡剂为有机硅消泡剂。The defoamer is an organosilicon defoamer.
(2)制备方法步骤如下：(2) the preparation method steps are as follows:
①将10kg的硬单体、5kg的软单体、2.6kg的功能性单体、0.5kg的乳化剂加入到A料罐中，搅拌0.9小时，搅拌速度为110转/min，进行预乳化，得到预乳化单体待用；①Add 10kg of hard monomer, 5kg of soft monomer, 2.6kg of functional monomer, and 0.5kg of emulsifier into the A material tank, stir for 0.9 hours, and the stirring speed is 110 rev/min to carry out pre-emulsification, The pre-emulsified monomer is obtained for use;
将11.2kg的软水和0.32kg引发剂加入到B料罐中，搅拌均匀，配成引发剂溶液，待用。Add 11.2kg of soft water and 0.32kg of initiator into the B material tank, stir evenly, and prepare an initiator solution for use.
②在反应釜中加入剩余的软水，2kg的PVOH母料，开启搅拌和加热装置，搅拌速度设定为80r/min，加热到90℃后，保温1.5小时，待PVOH母料完全溶解，加入1.8kg的预乳化单体，0.33kg的引发剂溶液，进行种子反应，反应时间1小时后，通过计量泵同时连续性加入配制好的预乳化单体和引发剂溶液，滴加时间控制为6小时，加料过程保持反应温度为90℃；待加料完成后，继续保温90℃2小时，然后降温到70℃，加入0.5kg的交联剂进行反应，反应1小时后，加入0.08kg的消泡剂充分搅拌，静置待冷却后，得到纸张用的 热封型丙烯酸乳液。②Add the remaining soft water and 2kg of PVOH masterbatch into the reaction kettle, turn on the stirring and heating device, set the stirring speed to 80r/min, heat to 90℃, keep the temperature for 1.5 hours, wait for the PVOH masterbatch to dissolve completely, add 1.8 kg of pre-emulsified monomer, 0.33 kg of initiator solution, and the seed reaction was carried out. After the reaction time was 1 hour, the prepared pre-emulsified monomer and initiator solution were continuously added simultaneously through the metering pump, and the dripping time was controlled to 6 hours. , the reaction temperature was kept at 90 °C during the feeding process; after the feeding was completed, the temperature was kept at 90 °C for 2 hours, then cooled to 70 °C, and 0.5 kg of crosslinking agent was added to react. After 1 hour of reaction, 0.08 kg of defoaming agent was added. After fully stirring and standing for cooling, a heat-sealing acrylic emulsion for paper is obtained.
将本发明实施例5提供的纸张用的热封型丙烯酸乳液，涂布在90g/m 2的原纸上，涂层干涂布量为4g/m 2，经热风烘干后，得到涂布纸；将制成的涂布纸进行检测，结果参见表5所示。 The heat-sealing acrylic emulsion for paper provided in Example 5 of the present invention was coated on a base paper of 90 g/m 2 , and the dry coating amount of the coating was 4 g/m 2 . After drying with hot air, a coated paper was obtained. ; Detect the coated paper made, and the results are shown in Table 5.
表5 应用本发明实施例5提供的纸张用的热封型丙烯酸乳液的涂布纸各项性能数据Table 5 Various performance data of coated paper using the heat-sealing acrylic emulsion for paper provided in Example 5 of the present invention
Figure PCTCN2021108884-appb-000011
Figure PCTCN2021108884-appb-000011
对比例1Comparative Example 1
采用现有丙烯酸乳液，具体为专利CN102321416A实施例2开发的产品，结构为80g/m 2原纸//4g/m 2丙烯酸乳液，即将上述丙烯酸乳液，涂布在80g/m 2的原纸上，涂层干涂布量为4g/m 2，经热风烘干后，得到涂布纸；将制成的涂布纸进行检测，结果参见表6所示。 Adopt the existing acrylic emulsion, specifically the product developed in the embodiment 2 of patent CN102321416A, the structure is 80g/m 2 base paper//4g/m 2 acrylic emulsion, that is, the above-mentioned acrylic emulsion is coated on 80 g/m 2 of base paper, coated The dry coating weight of the layer was 4 g/m 2 , and after drying with hot air, the coated paper was obtained;
表6 应用对比例1提供的丙烯酸乳液的涂布纸各项性能数据Table 6 Various performance data of the coated paper using the acrylic emulsion provided in Comparative Example 1
Figure PCTCN2021108884-appb-000012
Figure PCTCN2021108884-appb-000012
对比例2Comparative Example 2
采用现有聚乳酸涂料，具体为专利CN103774490A实施例1中的聚乳酸涂料，结构为80g/m 2原纸//4g/m 2聚乳酸涂料，即将上述聚乳酸涂料，涂布在80g/m 2的原纸上，涂层干涂布量为4g/m 2，经热风烘干后，得到涂布纸；将制成的涂布纸进行检测，结果参见表7所示。 Using the existing polylactic acid coating, specifically the polylactic acid coating in the embodiment 1 of patent CN103774490A, the structure is 80g/m 2 base paper//4g/m 2 polylactic acid coating, that is, the above-mentioned polylactic acid coating is coated on 80g/m 2 On the base paper, the dry coating weight of the coating was 4g/m 2 , and after drying with hot air, the coated paper was obtained;
表7 应用对比例2提供的聚乳酸涂料的涂布纸各项性能数据Table 7 Various performance data of the coated paper of the polylactic acid coating provided by the comparative example 2
Figure PCTCN2021108884-appb-000013
Figure PCTCN2021108884-appb-000013
Figure PCTCN2021108884-appb-000014
Figure PCTCN2021108884-appb-000014
通过比较可知，应用本发明的丙烯酸乳液制成的涂布纸热封性能优异，并且本发明提供的制备方法工艺简单、成本低，非常适合工业化生产。It can be seen from the comparison that the coated paper prepared by applying the acrylic emulsion of the present invention has excellent heat-sealing performance, and the preparation method provided by the present invention has simple process and low cost, and is very suitable for industrial production.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种纸张用的热封型丙烯酸乳液，由包括以下组分的原料制得：A heat-sealing acrylic emulsion for paper is prepared from the raw materials comprising the following components:
    PVOH母料2～5wt％；PVOH masterbatch 2～5wt%;
    硬单体7～12wt％；Hard monomer 7～12wt%;
    软单体5～9wt％；Soft monomer 5～9wt%;
    功能性单体1～3wt％；Functional monomer 1～3wt%;
    乳化剂0.3～0.6wt％；Emulsifier 0.3～0.6wt%;
    引发剂0.2～0.5wt％；Initiator 0.2～0.5wt%;
    交联剂0.3～0.5wt％；Crosslinking agent 0.3～0.5wt%;
    消泡剂0.05～0.1wt％；Defoamer 0.05～0.1wt%;
    余量的水；surplus water;
    所述功能性单体为乙烯基磺酸和/或丙烯酰胺；The functional monomer is vinylsulfonic acid and/or acrylamide;
    所述交联剂为氮丙啶和/或咪唑。The cross-linking agent is aziridine and/or imidazole.
  2. 根据权利要求1所述的纸张用的热封型丙烯酸乳液，其特征在于，所述PVOH母料的聚合度为400～1900，醇解度为88％～99％。The heat-sealing acrylic emulsion for paper according to claim 1, wherein the degree of polymerization of the PVOH masterbatch is 400-1900, and the degree of alcoholysis is 88%-99%.
  3. 根据权利要求1所述的纸张用的热封型丙烯酸乳液，其特征在于，所述硬单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯和苯乙烯中的一种或多种。The heat-sealing acrylic emulsion for paper according to claim 1, wherein the hard monomer is selected from one or more of methyl methacrylate, ethyl methacrylate and styrene.
  4. 根据权利要求1所述的纸张用的热封型丙烯酸乳液，其特征在于，所述软单体选自丙烯酸乙酯、甲基丙烯酸月桂酯和甲基丙烯酸正辛酯中的一种或多种。The heat-sealing acrylic emulsion for paper according to claim 1, wherein the soft monomer is selected from one or more of ethyl acrylate, lauryl methacrylate and n-octyl methacrylate .
  5. 根据权利要求1所述的纸张用的热封型丙烯酸乳液，其特征在于，所述乳化剂为十二烷基硫酸钠。The heat-sealing acrylic emulsion for paper according to claim 1, wherein the emulsifier is sodium lauryl sulfate.
  6. 根据权利要求1所述的纸张用的热封型丙烯酸乳液，其特征在于，所述引发剂为叔丁基过氧化氢。The heat-sealing acrylic emulsion for paper according to claim 1, wherein the initiator is tert-butyl hydroperoxide.
  7. 一种权利要求1～6任一项所述的纸张用的热封型丙烯酸乳液的制备方法，包括以下步骤：A preparation method of the heat-sealing acrylic emulsion for paper according to any one of claims 1 to 6, comprising the following steps:
    a)将硬单体、软单体、功能性单体、乳化剂混合，进行预乳化，得到预乳化单体；a) mixing hard monomer, soft monomer, functional monomer and emulsifier, and pre-emulsification to obtain pre-emulsified monomer;
    将第一用量的水和引发剂混合，得到引发剂溶液；Mix the first amount of water with an initiator to obtain an initiator solution;
    b)将PVOH母料用剩余的水溶解后，加入第二用量的预乳化单体和第三用量的引发剂溶液，进行种子反应；再通过计量泵同时连续性加入剩余的预乳化单体和引发剂溶液，滴加时间控制为6h～8h；待加料完成后，进行聚合反应，然后降温至70℃～75℃，加入交联剂进行交联反应，最后加入消泡剂充分搅拌，静置待冷却后得到纸张用的热封型丙烯酸乳液。b) after dissolving the PVOH masterbatch with the remaining water, add the second amount of pre-emulsion monomer and the third amount of initiator solution to carry out seed reaction; then continuously add the remaining pre-emulsion monomer and Initiator solution, the dropping time is controlled to be 6h ~ 8h; after the addition of materials is completed, the polymerization reaction is carried out, then the temperature is lowered to 70 ° C ~ 75 ° C, the cross-linking agent is added to carry out the cross-linking reaction, and finally the defoaming agent is added to fully stir and let stand After cooling, a heat-sealing acrylic emulsion for paper is obtained.
  8. 根据权利要求7所述的制备方法，其特征在于，步骤a)中所述预乳化的过程在搅拌下进行；所述预乳化的搅拌速度为100r/min～150r/min，时间为0.5h～1h；The preparation method according to claim 7, wherein the pre-emulsification process in step a) is carried out under stirring; the stirring speed of the pre-emulsification is 100r/min～150r/min, and the time is 0.5h～ 1h;
    所述第一用量的水占水总量的8～20wt％。The first amount of water accounts for 8-20 wt % of the total amount of water.
  9. 根据权利要求7所述的制备方法，其特征在于，步骤b)中所述第二用量的预乳化单体占预乳化单体总量的8～12wt％；The preparation method according to claim 7, wherein the second amount of the pre-emulsified monomer in step b) accounts for 8-12 wt% of the total amount of the pre-emulsified monomer;
    所述第三用量的引发剂溶液占引发剂溶液总量的2～4wt％。The third amount of the initiator solution accounts for 2-4 wt % of the total amount of the initiator solution.
  10. 根据权利要求7所述的制备方法，其特征在于，步骤b)中所述种子反应的温度为80℃～90℃，搅拌速度为80r/min～130r/min，时间为1h～2h；The preparation method according to claim 7, wherein the temperature of the seed reaction in step b) is 80°C to 90°C, the stirring speed is 80r/min to 130r/min, and the time is 1h to 2h;
    所述加入剩余的预乳化单体和引发剂溶液的过程保持温度为80℃～90℃；During the process of adding the remaining pre-emulsified monomer and initiator solution, the temperature is maintained at 80°C to 90°C;
    所述聚合反应的温度为80℃～90℃，搅拌速度为80r/min～130r/min，时间为1h～2h；The temperature of the polymerization reaction is 80℃～90℃, the stirring speed is 80r/min～130r/min, and the time is 1h～2h;
    所述交联反应的搅拌速度为80r/min～130r/min，时间为0.5h～1h。The stirring speed of the cross-linking reaction is 80r/min～130r/min, and the time is 0.5h～1h.
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