TWI759262B - Method of preparing super absorbent polymer - Google Patents

Abstract

Provided is a method of preparing super absorbent polymer. The method comprising the steps of: preparing a hydrogel crosslinked polymer by polymerizing a monomer composition including hydrophilic monomers, a crosslinking agent and a polymerization initiator; pulverizing the hydrogel crosslinked polymer; drying the pulverized hydrogel crosslinked polymer; preparing a base resin by pulverizing the dried hydrogel crosslinked polymer; and mixing the base resin with at least one of compounds represented by Formula (1) below and a surface-crosslinking agent to surface-crosslink the base resin: X-(Ra)_p(Rb)_q-Y ---- (1)

Description

製備超吸收聚合物之方法 Process for making superabsorbent polymers

本申請案主張於2015年3月30日申請之韓國專利申請案第10-2015-0044165號案及於2016年3月2日申請之韓國專利申請案第10-2016-0025114號案之優先權，及自此等產生之所有利益，此等案之揭露在此被完整併入以供參考。 This application claims the priority of Korean Patent Application No. 10-2015-0044165 filed on March 30, 2015 and Korean Patent Application No. 10-2016-0025114 filed on March 2, 2016 , and all benefits arising therefrom, the disclosures of these cases are hereby incorporated by reference in their entirety.

背景 background 1.領域 1. Field

本發明係有關於一種製備超吸收聚合物之方法。 The present invention relates to a method for preparing superabsorbent polymers.

2.相關技藝說明 2. Relevant technical description

超吸收聚合物(SAPs)係具有吸收其等本身重量之500至1000倍的水分之功能的合成聚合物材料，且依發展者不同地命名為超吸收材料(SAM)、吸收性凝膠材料(AGM)等。此等超吸收聚合物已被廣泛地作為用於土壤之保水劑、用於土木工程及結構之止水帶、用於播種之片材，及用於食物流通之物品，與諸如用於嬰兒紙尿布之衛生物品的領域之材料，因為其等開始進入實際使用。 Superabsorbent polymers (SAPs) are synthetic polymer materials that have the function of absorbing 500 to 1000 times their own weight in water, and are named as superabsorbent materials (SAM), absorbent gel materials ( AGM) etc. These superabsorbent polymers have been widely used as water-retaining agents for soils, waterstops for civil engineering and structures, sheets for sowing, and articles for food distribution, and products such as baby paper The material in the field of sanitary articles for diapers, as it began to enter practical use.

作為製備超吸收聚合物之方法，已知係逆相懸浮聚合反應或水溶液聚合反應。例如，逆相懸浮聚合反應係 揭露於JP-A-56-161408、JP-A-57-158209，及JP-A-57-198714。作為水溶液聚合反應，藉由加熱一水溶液而實施聚合反應之熱聚合反應、藉由以紫外線照射一水溶液而實施聚合反應之光聚合反應等係已知。 As a method for producing a superabsorbent polymer, a reverse-phase suspension polymerization reaction or an aqueous solution polymerization reaction is known. For example, reversed-phase suspension polymerization Disclosed in JP-A-56-161408, JP-A-57-158209, and JP-A-57-198714. As aqueous solution polymerization, thermal polymerization in which polymerization is performed by heating an aqueous solution, photopolymerization in which polymerization is performed by irradiating an aqueous solution with ultraviolet rays, and the like are known.

概要 summary

於製備超吸收聚合物之方法，產生水溶性組份，其係未經交聯之聚合物，及殘餘單體。水溶性組份及殘餘單體之含量係依聚合反應起始劑之含量、聚合反應溫度、內部交聯劑之含量、表面交聯條件等而改變。 In the process of making superabsorbent polymers, a water-soluble component, which is the uncrosslinked polymer, and residual monomers are produced. The content of water-soluble components and residual monomers varies depending on the content of the polymerization initiator, the polymerization temperature, the content of the internal cross-linking agent, and the surface cross-linking conditions.

當水溶性組份及殘餘單體之含量高時，尿布表面變黏或其液體滲透性會被降低，且會造成皮膚疾病及臭味。 When the content of water-soluble components and residual monomers is high, the surface of the diaper becomes sticky or its liquid permeability is reduced, and skin diseases and odors are caused.

本發明之各方面係提供一種製備超吸收聚合物之方法，藉此可獲得含有小量殘餘單體之一超吸收聚合物。 Aspects of the present invention provide a method of making a superabsorbent polymer whereby a superabsorbent polymer containing a small amount of residual monomer can be obtained.

但是，本發明之各方面係不限於此處所述者。本發明之上述及其它方面藉由參考於下提供之本發明詳細說明，對熟習與本發明有關之技術者會變得更顯見。 However, aspects of the present invention are not limited to those described herein. The above and other aspects of the present invention will become more apparent to those skilled in the art to which the present invention pertains by reference to the detailed description of the present invention provided below.

依據本發明之一例示實施例，提供一種用於製備超吸收聚合物之方法。此方法包含步驟：藉由使含有親水性單體、一交聯劑，及一聚合反應起始劑之一單體組成物聚合而製備一水凝膠交聯聚合物；使水凝膠交聯聚合物粉碎；使經粉碎之水凝膠交聯聚合物乾燥；藉由使經乾燥之水凝膠交聯聚合物粉碎而製備一基底樹脂；及使此基底樹脂與以如下化學式(1)表示之化合物之至少一者及一表面交 聯劑混合而使基底樹脂表面交聯。 According to an exemplary embodiment of the present invention, a method for preparing a superabsorbent polymer is provided. The method comprises the steps of: preparing a hydrogel cross-linked polymer by polymerizing a monomer composition containing a hydrophilic monomer, a cross-linking agent, and a polymerization initiator; cross-linking the hydrogel pulverizing the polymer; drying the pulverized hydrogel cross-linked polymer; preparing a base resin by pulverizing the dried hydrogel cross-linked polymer; and making the base resin with the following chemical formula (1) at least one of the compounds and a surface cross A linking agent is mixed to crosslink the surface of the base resin.

於一例示實施例，聚合反應起始劑可為一光聚合反應起始劑、一熱聚合反應起始劑，及一氧化還原起始劑之至少一者。 In an exemplary embodiment, the polymerization initiator may be at least one of a photopolymerization initiator, a thermal polymerization initiator, and a redox initiator.

於一例示實施例，此方法可進一步包含製備此單體組成物，製備此單體組成物可包括製備含有親水性單體及一中和劑之一第一組成物；藉由使第一組成物與交聯劑及聚合反應起始劑混合製備一第二組成物。 In an exemplary embodiment, the method may further comprise preparing the monomer composition, and preparing the monomer composition may include preparing a first composition comprising a hydrophilic monomer and a neutralizing agent; by making the first composition The compound is mixed with a crosslinking agent and a polymerization initiator to prepare a second composition.

於一例示實施例，使基底樹脂表面交聯可進一步包括使經表面處理之基底樹脂乾燥。 In an exemplary embodiment, surface-crosslinking the base resin may further include drying the surface-treated base resin.

X-(Ra)_p(Rb)_q-Y----(1) X-(Ra) _p (Rb) _q -Y----(1)

於化學式(1)，X係一不飽和烴基團或其一衍生物；Ra及Rb每一者獨立地係C_1-5之一伸烷基基團(-(CH₂)_m-，m係1至5整數)、C_1-4之一伸烷氧基基團(-(CH₂)_m-O-，m係1至4之整數)、C_2-6之一伸烯基基團(-(CH=CH)_m-，m係1至3之整數)、C_2-6之一伸烷(氧)基羰基基團(-(R_f)_o-(C=O)-(R'_f)_p-，o及p每一者獨立地係0至2之整數且不會同時為0，且R_f及R'_f每一者獨立地係C_1-5之一烴基團，或其一衍生物)、C_2-5之一羰氧基基團(-(R_g)_r-(C=O)-O-，r係0至2之整數，且R_g係C_1-4之一烴基團，或其一衍生物)，及C_2-6之一環狀羰氧基基團(-(CH₂)_s-(C=O)-O-(CH₂)_t-，s及t每一者獨立地係0至3之整數，且s及t之總合係1至5)之至少一者之一個二價原子基團。 In chemical formula (1), X is an unsaturated hydrocarbon group or a derivative thereof; each of Ra and Rb is independently a C _1-5 alkylene group (-(CH ₂ ) _m -, m is 1 to 5 integers), an alkeneoxy group of C _1-4 (-(CH ₂ ) _m -O-, m is an integer of 1 to 4), an alkenyl group of C _2-6 (-(CH 2 ) =CH) _m -, m is an integer from 1 to 3), an alkane (oxy) carbonyl group of C _2-6 (-(R _f ) _o -(C=O)-(R' _f ) _p - , o and p are each independently an integer from 0 to 2 and not simultaneously 0, and each of _Rf and _R'f is independently a _C1-5 hydrocarbon group, or a derivative thereof) , a carbonyloxy group of C _2-5 (-(R _g ) _r -(C=O)-O-, r is an integer from 0 to 2, and R _g is a hydrocarbon group of C _1-4 , or a derivative thereof), and a C _2-6 cyclic carbonyloxy group (-(CH ₂ ) _s -(C=O)-O-(CH ₂ ) _t -, each of s and t is independently an integer from 0 to 3, and the sum of s and t is a divalent atomic group of at least one of 1 to 5).

於化學式(1)，p可為2至10之整數，q可為0至10 之整數，且Y係一氫原子或一親水性基團。親水性基團可為一羥基基團(-OH)、一羧基基團(-COOH)，及一胺基基團((-NHR_h、-NH₂，或-NR_h2，R_h係C_1-5之一烴基團)之任一者。特別地，Y可為氫原子或羥基基團。 In chemical formula (1), p may be an integer of 2 to 10, q may be an integer of 0 to 10, and Y is a hydrogen atom or a hydrophilic group. The hydrophilic group can be a hydroxyl group (-OH), a carboxyl group (-COOH), and an amine group ((-NHR _h , -NH ₂ , or -NR _h2 , _Rh is C _{1 )} - Any one of ₅ a hydrocarbon group). In particular, Y can be a hydrogen atom or a hydroxyl group.

X可為C_2-5之一(甲基)乙烯基基團(CH₂=CR_a-，R_a係一氫原子，或C_1-3之一烴基團，或其一衍生物)、C_3-5之一(甲基)烯丙基基團(CH₂=CR_b-CH₂-，R_b係一氫原子，或C_1-2之一烴基團，或其一衍生物)、C_1-5之一醯基基團(R_cC(=O)-，R_c係一氫原子，或C_1-4之一烴基團，或其一衍生物)、C_3-5之一(甲基)丙烯醯基基團(CH₂=CR_d-C(=O)-，R_d係一氫原子，或C_1-2之一烴基團，或其一衍生物)，及C_3-5之一(甲基)丙烯醯氧基基團(CH₂=CR_e-C(=O)-O-，R_e係一氫原子，或C_1-2之一烴基團，或其一衍生物)之至少一者之一單價原子基團。 X can be a (methyl) vinyl group of C _2-5 (CH ₂ =CR _a -, R _a is a hydrogen atom, or a hydrocarbon group of C _1-3 , or a derivative thereof), C One of _3-5 (methyl) allyl groups (CH ₂ =CR _b -CH ₂ -, R _b is a hydrogen atom, or one of C _1-2 hydrocarbon groups, or a derivative thereof), C One of _1-5 acyl group (R _c C(=O)-, R _c is a hydrogen atom, or one of C _1-4 hydrocarbon group, or one of its derivatives), one of C _3-5 ( Meth)acryloyl group (CH ₂ =CR _d -C(=O)-, R _d is a hydrogen atom, or a hydrocarbon group of C _1-2 , or a derivative thereof), and C _3- One of ₅ (meth)acryloyloxy groups (CH ₂ =CR _e -C(=O)-O-, R _e is a hydrogen atom, or one of C _1-2 hydrocarbon groups, or a derivative thereof A monovalent atomic group of at least one of substances).

於一例示實施例，以化學式(1)表示之化合物至少一者可為以如下化學式(2)表示之化合物之至少一者：

In an exemplary embodiment, at least one of the compounds represented by the chemical formula (1) may be at least one of the compounds represented by the following chemical formula (2):

於化學式(2)，R₁可為C_1-2之一烷基基團及C_1-2之一烷氧基基團之任一者；R₂可為C_1-5之一伸烷基基團 (-(CH₂)_m-，m係1至5)、C_1-5之一伸烷氧基基團(-(CH₂)_m-O-，m係1至5之整數)，及C_2-6之一環狀羰氧基基團(-(CH₂)_s-(C=O)-O-(CH₂)_t-，s及t每一者獨立地係0至3之整數，且s及t之總合係1至5)之任一者；Y可為一氫原子及一羥基基團(-OH)之任一者；且n可為1至10之整數。 In chemical formula (2), R ₁ can be any one of an alkyl group of C _1-2 and an alkoxy group of C _1-2 ; R ₂ can be an alkylene group of C _1-5 group (-(CH ₂ ) _m -, m is 1 to 5), an alkoxy group of C _1-5 (-(CH ₂ ) _m -O-, m is an integer of 1 to 5), and C A cyclic carbonyloxy group of _2-6 (-( _CH2 ) _s- (C=O)-O-( _CH2 ) _t- , each of s and t is independently an integer from 0 to 3, And the sum of s and t is any one of 1 to 5); Y can be any one of a hydrogen atom and a hydroxyl group (—OH); and n can be an integer of 1 to 10.

於一例示實施例，以化學式(2)表示之化合物之至少一者可為以化學式(3)至(22)表示之化合物之至少一者：

In an exemplary embodiment, at least one of the compounds represented by the chemical formula (2) may be at least one of the compounds represented by the chemical formulas (3) to (22):

依據本發明之製備超吸收聚合物之方法，可獲得含有一小量之水溶性組份(可萃取份量：EC)及殘餘單體(RM)且展現改良之離心滯留能力(CRC)之一超吸收聚合物。 According to the method for preparing superabsorbent polymers of the present invention, it is possible to obtain a superabsorbent that contains a small amount of water-soluble components (extractable fraction: EC) and residual monomers (RM) and exhibits an improved centrifugal retention capacity (CRC). Absorbent polymer.

本發明之功效不限於前述，且其它各種功效於此處係被預期。 The effects of the present invention are not limited to the foregoing, and various other effects are contemplated herein.

P1‧‧‧製備單體組成物 P1‧‧‧Preparation of monomer composition

P11‧‧‧製備包括親水性單體及中和劑之第一組成物 P11‧‧‧Preparation of first composition including hydrophilic monomer and neutralizing agent

P12‧‧‧藉由使第一組成物與交聯劑及聚合反應起始劑混合製備第二組成物 P12‧‧‧Preparation of the second composition by mixing the first composition with the crosslinking agent and the polymerization initiator

P2‧‧‧製備水凝膠交聯聚合物 P2‧‧‧Preparation of hydrogel cross-linked polymer

P3‧‧‧使水凝膠交聯聚合物粉碎 P3‧‧‧Pulverize the hydrogel cross-linked polymer

P4‧‧‧使經粉碎之水凝膠交聯聚合物乾燥 P4‧‧‧Drying the crushed hydrogel cross-linked polymer

P5‧‧‧藉由使經乾燥之水凝膠交聯聚合物粉碎製備基底樹脂 P5‧‧‧Preparation of base resin by pulverizing dried hydrogel cross-linked polymer

P6‧‧‧使基底樹脂表面交聯 P6‧‧‧Crosslinking the surface of the base resin

P61‧‧‧使基底樹脂與以如下化學式(1)表示之化合物之至少一者及表面交聯劑混合X-(Ra)_p(Rb)_q-Y----(1) P61‧‧‧Mix the base resin with at least one of the compounds represented by the following chemical formula (1) and a surface crosslinking agent X-(Ra) _p (Rb) _q -Y----(1)

P62‧‧‧使經表面處理之基底樹脂乾燥 P62‧‧‧Dry the surface-treated base resin

圖式簡要說明 Brief description of the diagram

本發明之上述及其它方面與特徵藉由參考所附圖式詳細說明其例示實施例會變得更顯見，其中：圖1係依據本發明一實施例之一種製造超吸收聚合物之方法的一示意流程圖。 The above and other aspects and features of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the accompanying drawings, wherein: FIG. 1 is a schematic diagram of a method of making a superabsorbent polymer according to an embodiment of the present invention flow chart.

實施例之詳細說明 DETAILED DESCRIPTION OF THE EMBODIMENTS

本發明之優點及特徵與完成此之方法藉由參考下列例示實施例之詳細說明及所附圖式會更輕易瞭解。但是，本發明可以許多不同實施例而實施，且不應被闡釋為限於此處所述之實施例。相反地，此等實施例被提供，使得本揭露會係詳盡及完全，且會將本發明之思想完全傳達給熟習此項技藝者，且本發明會僅藉由所附之申請專利範圍界定。 The advantages and features of the present invention and the method of accomplishing this will be more readily understood by reference to the following detailed description of illustrative embodiments and the accompanying drawings. However, the present invention may be practiced in many different embodiments and should not be construed as limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art, and the invention will be defined only by the appended claims.

雖然術語“第一、第二等”文用以說明不同組成元素，此等組成元素並不受此術語所限制。此術語僅係用以使一構成元素與其它構成元素作區別。因此，於下列說明， 一第一組成元素可為一第二組成元素。 Although the terms "first, second, etc." are used to describe various constituent elements, these constituent elements are not limited by this term. This term is only used to distinguish a constituent element from other constituent elements. Therefore, in the following description, A first constituent element may be a second constituent element.

於本說明書中，“C_A-B”意指碳原子之數量係A至B。例如，“C_1-5烷基基團”係具有1至5個碳原子之一烷基基團。於本說明書中，“C及/或D”係定義為C、D，或C及D。於本說明書中，“E至F”係定義為E或更多及F或更少。 In this specification, "C _AB " means the number series A to B of carbon atoms. For example, a " _C1-5 alkyl group" is an alkyl group having one of 1 to 5 carbon atoms. In this specification, "C and/or D" is defined as C, D, or C and D. In this specification, "E to F" is defined as E or more and F or less.

於本說明書中，“不飽和烴基團”係定義為藉由自具有一不飽和鍵之一烴移除一氫原子而獲得之一殘餘物的一單價原子基團。不飽和烴基團之例子可包括一(甲基)乙烯基基團及一(甲基)烯丙基基團。 In this specification, "unsaturated hydrocarbon group" is defined as a monovalent atomic group obtained by removing a hydrogen atom from a hydrocarbon having an unsaturated bond to obtain a residue. Examples of unsaturated hydrocarbon groups may include a mono(methyl)vinyl group and a mono(meth)allyl group.

於本說明書中，“烷基基團”包括一線性或分支之烷基基團，且其例子可包括一正丁基基團及一第三丁基基團。於本說明書中，“(甲基)乙烯基基團”係於其端部具有一雙鍵之一單價原子基團，且係以CH₂=CR_a-表示。於乙烯基基團，R_a係一氫原子，且於甲基乙烯基基團，R_a係一烷基基團。於本說明書中，“(甲基)烯丙基基團”係於其端部具有一雙鍵之一單價原子基團，且係以CH₂=CR_b-CH₂-表示。於烯丙基基團，R_b係一氫原子，且於甲基烯丙基基團，R_b係一烷基基團。 In this specification, "alkyl group" includes a linear or branched alkyl group, and examples thereof may include an n-butyl group and a tertiary butyl group. In this specification, "(methyl)vinyl group" is a monovalent atom group having a double bond at its terminal, and is represented by CH ₂ =CR _a -. In the case of vinyl groups, _Ra is a hydrogen atom, and in the case of methylvinyl groups, _Ra is an alkyl group. In this specification, the "(meth)allyl group" is a monovalent atom group having a double bond at its terminal, and is represented by CH ₂ =CR _b -CH ₂ -. In an allyl group, R _b is a hydrogen atom, and in a methallyl group, R _b is an alkyl group.

於本說明書中，“G衍生物”係定義為G之不飽和烴基團或烷基基團之一些或所有的氫原子係以排除碳原子及氫原子之其它原子，或含有排除碳原子及氫原子之其它原子之原子基團，諸如，氧(O)、氮(N)、一羰基基團(-(C=O)-)、一醯基基團(R_cC(=O)-)，及一(甲基)丙烯醯基基團(CH₂=CR_d-C(=O)-)，取代之一衍生物。 In this specification, a "G derivative" is defined as an unsaturated hydrocarbon group or alkyl group of G in which some or all of the hydrogen atoms are excluding carbon atoms and other atoms of hydrogen atoms, or contain other atoms excluding carbon atoms and hydrogen atoms. Atomic groups of other atoms such as oxygen (O), nitrogen (N), a carbonyl group (-(C=O)-), a monoacyl group (R _c C(=O)-) , and a (meth)acryloyl group (CH ₂ =CR _d -C(=O)-), substituted for one of the derivatives.

於本說明書中，“烷氧基基團”係其中一烷基基團係與一氧原子鍵結且係一烷基基團之衍生物的一單價原子基團。烷基基團可為一線性或分支之烷基基團。於本說明書中，“醯基基團”係其中一羰基基團係與一烴基團或其一衍生物鍵結之一單價原子基團，且係以R_cC(=O)-表示。於醯基基團，R_c係一氫原子，或C_1-5之一烴基團及其一衍生物。於本說明書中，“(甲基)丙烯醯基基團”係其中一(甲基)乙烯基基團係與一羰基基團鍵結，且係以CH₂=CR_d-C(=O)-表示之一單價原子基團。於丙烯醯基基團，R_d可為一氫原子，且於甲基丙烯醯基基團，R_d可為一烷基基團等。於本說明書中，“(甲基)丙烯醯氧基基團”係其中一(甲基)丙烯醯基基團係與一氧原子鍵結，且係以CH₂=CR_e-C(=O)-O-表示之一單價原子基團。於丙烯醯氧基基團，R_e可為一氫原子，且於甲基丙烯醯氧基基團，R_d可為一烷基基團等。 In this specification, an "alkoxy group" is a monovalent atomic group in which an alkyl group is bonded to an oxygen atom and is a derivative of an alkyl group. The alkyl group can be a linear or branched alkyl group. In this specification, "acyl group" is a monovalent atomic group in which a carbonyl group is bonded to a hydrocarbon group or a derivative thereof, and is represented by R _c C(=O)-. For the acyl group, R _c is a hydrogen atom, or a hydrocarbon group of C _1-5 and a derivative thereof. In this specification, a "(meth)acryloyl group" refers to a group in which a (meth)vinyl group is bonded to a carbonyl group, and is represented by CH ₂ =CR _d -C(=O) - represents a monovalent atomic group. In an acryl group, R _d can be a hydrogen atom, and in a methacryloyl group, R _d can be an alkyl group, and the like. In this specification, a "(meth)acryloyloxy group" is one in which a (meth)acryloyl group is bonded to an oxygen atom, and is represented by CH ₂ =CR _e -C(=O )-O- represents a monovalent atomic group. In an acryloxy group, R _e may be a hydrogen atom, and in a methacryloyloxy group, R _d may be an alkyl group and the like.

於本說明書中，“伸烷基基團”係由碳原子及氫原子組成之一個二價原子基團，且係以-(CH₂)_m-表示。伸烷基基團之例子可包括一伸甲基基團(-CH₂-)、一伸乙基基團(-CH₂CH₂-)等。於本說明書中，“伸烷氧基基團”係其中一伸烷基基團係與一氧原子鍵結之一個二價原子基團，且係以-(CH₂)_m-O-表示。伸烷氧基基團之例子可包括一伸甲氧基基團(-CH₂O-、-OCH₂-)、一伸乙氧基基團(-CH₂CH₂O-、-OCH₂CH₂-)等。於本說明書中，“伸烷基(氧)羰基基團”係其中一伸烷(氧)基基團係與一羰基基團鍵結之一個二價原子基團，且係以-(R_f)_o-(C=O)-(R'_f)_p-表示。伸烷(氧)基羰基基 團之例子可包括一伸甲基羰基基團(-CH₂-(C=O)-)、一伸甲基羰氧基基團(-CH₂-(C=O)-CH₂-)、一伸甲氧基羰基基團(-CH₂-O-(C=O)-)、一個二伸甲氧基羰基基團(-CH₂-O-(C=O)-OCH₂-、-OCH₂-(C=O)-CH₂-O-)等。於本說明書中，“羰氧基基團”係其中一羰基基團係與一氧原子鍵結之一個二價原子基團，且係以-(R_g)_r-(C=O)-O-表示。羰氧基基團之例子可包括一羰氧基基團(-(C=O)-O-)、一伸甲基羰氧基基團(-CH₂-(C=O)-O-)等。於本說明書中，“環狀羰氧基基團”係藉由自一環狀酯移除二個氫原子而獲得之一殘餘物，係一個二價原子基團，且係以-(CH₂)_s-(C=O)-O-(CH₂)_t-表示。環狀羰氧基基團之例子可包括諸如己內酯之一個二價原子基團。 In this specification, the "alkylene group" is a divalent atomic group consisting of carbon atoms and hydrogen atoms, and is represented by -(CH ₂ ) _m -. Examples of alkylene groups may include a methylene group ( _-CH2- ), an ethylidene group ( _{-CH2CH2- )} , and the like. In this specification, the "alkeneoxy group" is a divalent atom group in which a monoalkylene group is bonded to an oxygen atom, and is represented by -(CH ₂ ) _m -O-. Examples of alkeneoxy groups may include a methoxy group (-CH ₂ O-, -OCH ₂ -), an ethoxy group (-CH ₂ CH ₂ O-, -OCH ₂ CH ₂ - )Wait. In this specification, "alkylene (oxy) carbonyl group" is a divalent atomic group in which a monoalkylene (oxy) group is bonded to a carbonyl group, and is represented by -(R _f ) _o -(C=O)-(R' _f ) _p - represents. Examples of alkylene(oxy)carbonyl groups may include a monomethylcarbonyl group ( _-CH2- (C=O)-), a monomethylcarbonyl group ( _-CH2- (C=O)- -CH ₂ -), a mono-methoxycarbonyl group (-CH ₂ -O-(C=O)-), a di-methoxycarbonyl group (-CH ₂ -O-(C=O)- OCH ₂ -, -OCH ₂ -(C=O)-CH ₂ -O-) and the like. In this specification, "carbonyloxy group" refers to a divalent atomic group in which a carbonyl group is bonded to an oxygen atom, and is represented by -(R _g ) _r -(C=O)-O -express. Examples of carbonyloxy groups may include a carbonyloxy group (-(C=O)-O-), a monomethylcarbonyloxy group (-CH ₂ -(C=O)-O-), and the like . In this specification, "cyclic carbonyloxy group" is a residue obtained by removing two hydrogen atoms from a cyclic ester, is a divalent atomic group, and is represented by -(CH ₂ ) _s -(C=O)-O-(CH ₂ ) _t - represents. Examples of cyclic carbonyloxy groups may include a divalent atom group such as caprolactone.

於本說明書中，“胺基基團”係藉由自氨移除一個氫原子而獲得之一殘餘物，且可以-NHR_h、-NH₂，或-NR_h2表示。於胺基基團，R_h可為一烷基基團等。 In this specification, an "amine group" is a residue obtained by removing one hydrogen atom from ammonia, and can be represented by -NHR _h , -NH ₂ , or -NR _h2 . For an amine group, R _h may be an alkyl group or the like.

圖1係依據本發明一實施例之一種製造超吸收聚合物之方法的示意流程圖。 FIG. 1 is a schematic flow chart of a method for manufacturing a superabsorbent polymer according to an embodiment of the present invention.

參考圖1，依據本發明一實施例之製備超吸收聚合物之方法包括步驟：(P1)製備一單體組成物；(P2)製備一水凝膠交聯聚合物；(P3)使水凝膠交聯聚合物粉碎；(P4)使經粉碎之水凝膠交聯聚合物乾燥；(P5)使經乾燥之水凝膠交聯聚合物粉碎成一基底樹脂；及(P6)使基底樹脂表面交聯。 1 , a method for preparing a superabsorbent polymer according to an embodiment of the present invention includes the steps of: (P1) preparing a monomer composition; (P2) preparing a hydrogel cross-linked polymer; (P3) making a hydrogel (P4) drying the pulverized hydrogel cross-linked polymer; (P5) pulverizing the dried hydrogel cross-linked polymer into a base resin; and (P6) making the base resin surface cross-linked.

製備單體組成物之步驟(P1)可包括步驟：(P11) 製備一第一組成物，其含有親水性單體及一中和劑；及(P12)使此第一組成物與一內部交聯劑及一聚合反應起始劑混合製備一第二組成物。於製備含有親水性單體及一中和劑之第一組成物之步驟(P11)，此第一組成物可包括所有之預定親水性單體，且亦可包括一些此等預定親水性單體。於後者之情況，其它之此等預定親水性單體可於使此第一組成物與一內部交聯劑及一聚合反應起始劑混合製備一第二組成物之步驟(P12)，與內部交聯劑及聚合反應起始劑一起添加至此第一組成物。 The step (P1) of preparing the monomer composition may include the step: (P11) A first composition is prepared, which contains a hydrophilic monomer and a neutralizing agent; and (P12) a second composition is prepared by mixing the first composition with an internal cross-linking agent and a polymerization initiator. In the step (P11) of preparing a first composition containing hydrophilic monomers and a neutralizing agent, the first composition may include all of the predetermined hydrophilic monomers, and may also include some of these predetermined hydrophilic monomers . In the latter case, other such predetermined hydrophilic monomers can be mixed with the first composition with an internal cross-linking agent and a polymerization initiator to prepare a second composition step (P12), and the internal A crosslinking agent and a polymerization initiator are added together to this first composition.

親水性單體可無受限地使用，只要其係一般用於製備超吸收聚合物之一單體。親水性單體係具有一親水性基團之一單體，且親水性基團之例子可包括一羥基基團(-OH)、一羧基基團(-COOH)，及一胺基基團(-NHR_h、-NH₂，或-NR_h2，此處，R_h可為C_1-5之一烷基基團等)。 The hydrophilic monomer can be used without limitation as long as it is one of the monomers typically used to prepare superabsorbent polymers. The hydrophilic monomer system has a monomer of a hydrophilic group, and examples of the hydrophilic group may include a hydroxyl group (-OH), a carboxyl group (-COOH), and an amine group ( -NHR _h , -NH ₂ , or -NR _{h 2} , where R _h can be one of C _1-5 alkyl groups, etc.).

親水性單體可為一水溶性之以不飽和乙烯為主之單體。水溶性之以不飽和乙烯為主之單體可為陰離子性單體及其等之鹽類、非離子性親水性單體，及含胺基基團之不飽和單體及其等之四級銨鹽類之至少一者。 The hydrophilic monomer may be a water-soluble unsaturated ethylene-based monomer. Water-soluble monomers mainly based on unsaturated ethylene can be anionic monomers and their salts, non-ionic hydrophilic monomers, and unsaturated monomers containing amine groups and their quaternary At least one of ammonium salts.

陰離子性單體及其鹽類之例子可包括丙烯酸、甲基丙烯酸、無水馬來酸、福馬酸、巴豆酸、衣康酸、2-丙烯醯基乙烷磺酸、2-甲基丙烯醯基乙烷磺酸、2-(甲基)丙烯醯基丙烷磺酸，及2-(甲基)丙烯醯胺-2-甲基丙烷磺酸。 Examples of anionic monomers and salts thereof may include acrylic acid, methacrylic acid, anhydrous maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acryloethanesulfonic acid, 2-methacryloic acid Ethanesulfonic acid, 2-(meth)acrylamidopropanesulfonic acid, and 2-(meth)acrylamido-2-methylpropanesulfonic acid.

非離子性親水性單體之例子可包括(甲基)丙烯醯胺、N-取代之(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸 酯、2-羥基丙基(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯，及聚乙二醇(甲基)丙烯酸酯。 Examples of non-ionic hydrophilic monomers may include (meth)acrylamides, N-substituted (meth)acrylates, 2-hydroxyethyl (meth)acrylic acid ester, 2-hydroxypropyl (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, and polyethylene glycol (meth)acrylate.

含胺基基團之不飽和單體及其等之四級銨鹽類之例子可包括(N,N)-二甲基胺基乙基(甲基)丙烯酸酯，及(N,N)-二甲基胺基丙基(甲基)丙烯醯胺。 Examples of amine group-containing unsaturated monomers and their quaternary ammonium salts may include (N,N)-dimethylaminoethyl (meth)acrylate, and (N,N)- Dimethylaminopropyl(meth)acrylamide.

單體組成物中之水溶性之以不飽和乙烯為主之單體的濃度可於考量聚合反應及反應條件(單體組成物之供料速率，及熱及/或光之照射時間、照射範圍，及照射強度等)而適當地選擇及使用。於例示實施例，水溶性之以不飽和乙烯為主之單體的濃度可為30重量%(wt%)至60重量%之範圍。 The concentration of the water-soluble unsaturated ethylene-based monomer in the monomer composition can be determined by considering the polymerization reaction and reaction conditions (the feed rate of the monomer composition, and the irradiation time and irradiation range of heat and/or light). , and irradiation intensity, etc.) and appropriately selected and used. In illustrative embodiments, the concentration of the water-soluble unsaturated ethylene-based monomer may range from 30% by weight (wt%) to 60% by weight.

中和劑係用以使親水性單體中和化。其典型例子可不受限地包括氫氧化鈉及碳酸氫鈉。中和劑可被使用，使得單體組成物之中和化程度係於65莫耳%至75莫耳%之範圍內。但是，本發明係不限於此。 Neutralizers are used to neutralize hydrophilic monomers. Typical examples thereof may include, without limitation, sodium hydroxide and sodium bicarbonate. Neutralizing agents can be used such that the degree of neutralization of the monomer composition is in the range of 65 mol% to 75 mol%. However, the present invention is not limited to this.

作為內部交聯劑，具有能與單體之一取代基反應之至少一官能性基團及至少一不飽和乙烯基團之一交聯劑，具有二或更多個可與單體之一取代基及/或藉由使單體水解而形成之一取代基反應之官能性基團之一交聯劑可被使用。 As an internal cross-linking agent, it has at least one functional group that can react with one of the substituents of the monomer and one of the cross-linking agents of at least one unsaturated vinyl group, and has two or more that can be substituted with one of the monomers. A crosslinking agent may be used as a functional group and/or a functional group that reacts by hydrolyzing the monomer to form a substituent.

於例示實施例，內部交聯劑之例子可包括C_8-12之雙丙烯醯胺、C_8-12之雙甲基丙烯醯胺、C_2-12之一多元醇之聚(甲基)丙烯酸酯，及C_2-10之一多元醇之聚(甲基)烯丙醚。 In illustrative embodiments, examples of internal crosslinking agents may include _C8-12 bisacrylamide, _C8-12 bismethacrylamide, _C2-12 polyol poly(methyl) Acrylates, and poly(meth)allyl ethers of C _2-10 polyols.

內部交聯劑之特別例子可不受限地包括(聚)乙二醇(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化(3)-三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化(6)-三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化(9)-三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化(15)-三羥甲基丙烷三(甲基)丙烯酸酯丙三醇三(甲基)丙烯酸酯、丙三醇丙烯酸酯甲基丙烯酸酯、2,2-雙[(丙烯氧基)甲基]丁基丙烯酸酯(3EO)、N,N'-伸甲基雙(甲基)丙烯酸酯、伸乙氧基(甲基)丙烯酸酯、聚伸乙氧基(甲基)丙烯酸酯、伸丙氧基(甲基)丙烯酸酯、丙三醇二丙烯酸酯、丙三醇三丙烯酸酯、三羥甲基三丙烯酸酯、三烯丙胺、三芳基氰尿酸酯、三烯丙基異氰酸酯、聚乙二醇、二乙二醇、丙二醇，及此等之二或更多種之混合物。 Specific examples of internal crosslinking agents may include, without limitation, (poly)ethylene glycol (meth)acrylate, (poly)propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, Ethoxylated (3)-Trimethylolpropane Tri(meth)acrylate, Ethoxylated (6)-Trimethylolpropane Tri(meth)acrylate, Ethoxylated (9)- Trimethylolpropane tri(meth)acrylate, ethoxylated (15)-trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, glycerol acrylate methyl Acrylate Acrylates, polyethoxylated (meth)acrylates, propoxylated (meth)acrylates, glycerol diacrylates, glycerol triacrylates, trimethylol triacrylates, trienes Propylamine, triarylcyanurate, triallyl isocyanate, polyethylene glycol, diethylene glycol, propylene glycol, and mixtures of two or more of these.

於例示實施例，以100重量分之親水性單體為基準，內部交聯劑可以0.01至0.5重量份之量包含，但不限於此。 In the exemplary embodiment, based on 100 parts by weight of the hydrophilic monomer, the internal cross-linking agent may be included in an amount of 0.01 to 0.5 parts by weight, but is not limited thereto.

聚合反應起始劑可為一光聚合反應起始劑、一熱聚合反應起始劑，及一氧化還原起始劑之至少一者。例如，作為聚合反應起始劑，光聚合反應起始劑及熱聚合反應起始劑二者可被使用。再者，例如，作為聚合反應起始劑，熱聚合反應起始劑及氧化還原起始劑二者可被使用。 The polymerization initiator may be at least one of a photopolymerization initiator, a thermal polymerization initiator, and a redox initiator. For example, as the polymerization initiator, both a photopolymerization initiator and a thermal polymerization initiator can be used. Furthermore, for example, as the polymerization initiator, both a thermal polymerization initiator and a redox initiator can be used.

光聚合反應起始劑會藉由照射紫外線而起始單體組成物之聚合反應，熱聚合反應起始劑會藉由加熱而起始單體組成物之聚合反應，且氧化還原起始劑會藉由氧化 還原反應起始單體組成物之聚合反應。當使用光聚合反應起始劑及熱聚合反應起始劑，單體組成物之聚合反應可藉由熱聚合反應起始劑，使用於光聚合反應期間產生之熱實施。當使用氧化還原起始劑及熱聚合反應起始劑，單體組成物之聚合反應可藉由熱聚合反應起始劑，使用於氧化還原反應期間產生之熱實施。 The photopolymerization initiator initiates the polymerization of the monomer composition by irradiating ultraviolet rays, the thermal polymerization initiator initiates the polymerization of the monomer composition by heating, and the redox initiator initiates the polymerization of the monomer composition. by oxidation The reduction reaction starts the polymerization of the monomer composition. When the photopolymerization initiator and the thermal polymerization initiator are used, the polymerization reaction of the monomer composition can be carried out by the thermal polymerization initiator using the heat generated during the photopolymerization reaction. When a redox initiator and a thermal polymerization initiator are used, the polymerization of the monomer composition can be carried out by the thermal polymerization initiator using the heat generated during the redox reaction.

聚合反應起始劑之例子可不受限地包括苯乙酮衍生物，諸如，二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、4-(2-羥基乙氧基)苯基-(2-羥基)-2-丙酮，及1-羥基環己基苯酮；安息香烷基醚類，諸如，安息香甲醚、安息香***、安息香異丙醚，及安息香異丁醚；二苯甲酮衍生物，諸如，甲基鄰-苯甲醯基苯甲酸酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基-二苯基硫醚，及(4-苯甲醯基-苯甲基)三甲基氯化銨；以9-氧硫

為主之化合物；醯基膦氧化物衍生物，諸如，雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物，及二苯基(2,4,6-三甲基苯甲醯基)-膦氧化物；偶氮化合物，諸如，2-羥基-甲基-丙腈，及2,2'-(偶氮-雙(2-甲基-N-(1,1'-雙(羥基甲基)-2-羥基乙基)丙醯胺)；及此等之混合物。此處，熱聚合反應起始劑不受特別限制，但其例子包括一以偶氮為主之起始劑、一以過氧化物為主之起始劑、一以氧化還原為主之起始劑，及一以有機鹵化物為主之起始劑。其等可單獨或以其等之二或更多者之混合物使用。熱聚合反應起始劑之特別例子可不受限地包括過硫酸鈉(Na₂S₂O₈)及過硫酸鉀(K₂S₂O₈)。 Examples of the polymerization initiator may include, without limitation, acetophenone derivatives such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-( 2-hydroxyethoxy)phenyl-(2-hydroxy)-2-propanone, and 1-hydroxycyclohexylphenone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and Benzoin isobutyl ether; benzophenone derivatives such as, methyl-o-benzylbenzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyl-dibenzoate Phenyl sulfide, and (4-benzyl-benzyl)trimethylammonium chloride; with 9-oxosulfur

The main compound; acylphosphine oxide derivatives, such as, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, and diphenyl(2,4,6-triphenylphosphine) methylbenzyl)-phosphine oxide; azo compounds such as, 2-hydroxy-methyl-propionitrile, and 2,2'-(azo-bis(2-methyl-N-(1, 1'-bis(hydroxymethyl)-2-hydroxyethyl)propionamide); and mixtures of these. Here, the thermal polymerization initiator is not particularly limited, but examples thereof include an azo-based The main initiator, a peroxide-based initiator, a redox-based initiator, and an organic halide-based initiator. These can be used alone or in combination A mixture of two or more of them is used. Specific examples of thermal polymerization initiators may include, without limitation, sodium persulfate (Na ₂ S ₂ O ₈ ) and potassium persulfate (K ₂ S ₂ O ₈ ).

若聚合反應起始功效可被展現，聚合反應起始劑之含量可適當地選擇。例如，以100重量份之親水性單體為基準，光聚合反應起始劑可以0.005至0.5重量份之量包括於單體組成物中，且以100重量份之親水性單體為基準，熱聚合反應起始劑可以0.01至0.5重量份之量包含於單體組成物中。 The content of the polymerization initiator may be appropriately selected if the polymerization initiation efficacy can be exhibited. For example, based on 100 parts by weight of the hydrophilic monomer, the photopolymerization initiator may be included in the monomer composition in an amount of 0.005 to 0.5 parts by weight, and based on 100 parts by weight of the hydrophilic monomer, the thermal The polymerization initiator may be included in the monomer composition in an amount of 0.01 to 0.5 parts by weight.

於使單體組成物聚合之步驟(P2)，一光聚合反應及/或一熱聚合反應係藉由對單體組成物施用光及/或熱而實施，或一氧化還原聚合反應被實施。例如，當單體組成物以紫外線照射時，一光聚合反應係藉由光聚合反應起始劑起始。於其中單體組成物包括光聚合反應起始劑及熱聚合反應起始劑之情況，熱聚合反應起始劑可使用於光聚合反應期間產生之熱起始一熱聚合反應。聚合反應可使用一帶型聚合反應器實施，且片狀水凝膠交聯聚合物可藉由此聚合反應獲得。 In the step (P2) of polymerizing the monomer composition, a photopolymerization reaction and/or a thermal polymerization reaction is performed by applying light and/or heat to the monomer composition, or a redox polymerization reaction is performed. For example, when the monomer composition is irradiated with ultraviolet rays, a photopolymerization reaction is initiated by a photopolymerization initiator. In the case where the monomer composition includes a photopolymerization initiator and a thermal polymerization initiator, the thermal polymerization initiator may be used to initiate a thermal polymerization reaction generated during the photopolymerization reaction. The polymerization reaction can be carried out using a belt type polymerization reactor, and the sheet-like hydrogel cross-linked polymer can be obtained by this polymerization reaction.

於使水凝膠交聯聚合物粉碎之步驟(P3)，此聚合反應完全後獲得之片狀水凝膠交聯聚合物係轉移至一切割器，且被細微或粗略地粉碎成一預定尺寸。片狀水凝膠交聯聚合物可被細微或粗略地粉碎成具有1公分至3公分之顆粒尺寸的一顆粒狀水凝膠交聯聚合物。使水凝膠交聯聚合物粉碎之步驟(P3)可使用一刀片式切割器、一砍切式切割器、一捏合式切割器、一震動式粉碎器、一衝擊式粉碎器，或一磨擦式粉碎器實施。顆粒狀水凝膠交聯聚合物之水含量可為，例如，約40重量%至約60重量%。 In the step (P3) of pulverizing the hydrogel cross-linked polymer, the sheet-like hydrogel cross-linked polymer obtained after the completion of the polymerization reaction is transferred to a cutter and finely or roughly pulverized into a predetermined size. The sheet-like hydrogel cross-linked polymer may be finely or coarsely pulverized into a granular hydrogel cross-linked polymer having a particle size of 1 cm to 3 cm. The step (P3) of pulverizing the hydrogel cross-linked polymer can use a blade cutter, a chopping cutter, a kneading cutter, a vibration pulverizer, an impact pulverizer, or a friction shredder implementation. The water content of the particulate hydrogel cross-linked polymer may be, for example, from about 40% to about 60% by weight.

於使經粉碎之水凝膠交聯聚合物乾燥之步驟(P4)，經粉碎之水凝膠交聯聚合物係於約150℃至約200℃之溫度乾燥約20分鐘至約60分鐘。例如，經粉碎之水凝膠交聯聚合物可藉由一熱空氣乾燥器、一流體床乾燥器、一空氣流乾燥器、一紅外線乾燥器，或一介電加熱乾燥器乾燥。 In the step (P4) of drying the pulverized hydrogel cross-linked polymer, the pulverized hydrogel cross-linked polymer is dried at a temperature of about 150°C to about 200°C for about 20 minutes to about 60 minutes. For example, the pulverized hydrogel cross-linked polymer can be dried by a hot air dryer, a fluid bed dryer, an air flow dryer, an infrared dryer, or a dielectric heating dryer.

使經乾燥之水凝膠交聯聚合物粉碎製備基底樹脂之步驟(P5)可包括使經乾燥之水凝膠交聯聚合物細微粉碎成具有微米(μm)之顆粒尺寸，例如，150μm至850μm之平均顆粒尺寸的顆粒之步驟。使經乾燥之水凝膠交聯聚合物粉碎製備基底樹脂之步驟(P5)可使用一刀片式切割器、一砍切式切割器、一捏合式切割器、一震動式粉碎器、一衝擊式粉碎器，或一磨擦式粉碎器實施。 The step (P5) of pulverizing the dried hydrogel cross-linked polymer to prepare the base resin may include finely pulverizing the dried hydrogel cross-linked polymer to have a particle size of micrometer (μm), for example, 150 μm to 850 μm the average particle size of the particles in the step. The step (P5) of pulverizing the dried hydrogel cross-linked polymer to prepare the base resin can use a blade cutter, a chopping cutter, a kneading cutter, a vibrating pulverizer, an impact cutter A shredder, or a friction shredder is implemented.

使基底樹脂表面交聯之步驟(P6)可包括：使基底樹脂與以化學式(1)表示之化合物的至少一者及一表面交聯劑混合之步驟(P61)；及使經表面處理之基底樹脂乾燥之步驟(P62)。 The step (P6) of surface-crosslinking the base resin may include: the step (P61) of mixing the base resin with at least one of the compounds represented by the chemical formula (1) and a surface crosslinking agent; and subjecting the surface-treated substrate Resin drying step (P62).

於使基底樹脂與以化學式(1)表示之化合物之至少一者及表面交聯劑混合之步驟(P61)，形成具有比基底樹脂更高交聯密度之一經表面交聯的層，藉此，提供具有一芯核結構之一經表面交聯之基底樹脂，其中，基底樹脂係作為一芯且經表面交聯之層係形成於基底樹脂之表面上。使基底樹脂與以化學式(1)表示之化合物之至少一者及表面交聯劑(若需要)混合之步驟(P61)可實施數次。 In the step (P61) of mixing the base resin with at least one of the compounds represented by the chemical formula (1) and the surface crosslinking agent, a surface-crosslinked layer having a higher crosslinking density than the base resin is formed, whereby, A surface-crosslinked base resin having a core-core structure is provided, wherein the base resin serves as a core and a surface-crosslinked layer is formed on the surface of the base resin. The step (P61) of mixing the base resin with at least one of the compounds represented by the chemical formula (1) and a surface crosslinking agent (if necessary) may be performed several times.

表面交聯劑之例子可不受限地包括烷基二元醇類、伸烷基二醇類、烷基二縮水甘油醚類、多價金屬類、乙二醇二縮水甘油醚類、伸烷基碳酸酯類，諸如，伸乙基碳酸酯，水，及乙醇。 Examples of surface crosslinking agents may include, without limitation, alkyl glycols, alkylene glycols, alkyl diglycidyl ethers, polyvalent metals, ethylene glycol diglycidyl ethers, alkylene Carbonates such as ethylene carbonate, water, and ethanol.

以如下化學式(1)表示之化合物之至少一者可藉由與未經交聯之線性聚合物鏈反應降低超吸收聚合物之可萃取份量(EC)的數值，且可藉由與未反應之單體反應降低超吸收聚合物之殘餘單體(RM)的濃度之數值。同時，超吸收之離心滯留能力(CRC)可藉由一親水性伸烷氧基基團改良。 At least one of the compounds represented by the following formula (1) can reduce the value of the extractable fraction (EC) of the superabsorbent polymer by reacting with the uncrosslinked linear polymer chain, and can reduce the value of the extractable content (EC) of the superabsorbent polymer by reacting with the unreacted linear polymer chain. The monomer reaction reduces the amount of residual monomer (RM) concentration of the superabsorbent polymer. Meanwhile, the centrifugal retention capacity (CRC) of superabsorbent can be improved by a hydrophilic alkyleneoxy group.

<化學式(1)>X-(Ra)_p(Rb)_q-Y <Chemical formula (1)> X-(Ra) _p (Rb) _q -Y

於化學式(1)，X係一不飽和烴基團或其一衍生物；且Ra及Rb每一者獨立地係C_1-5之一伸烷基基團(-(CH₂)_m-，m係1至5之整數)、C_1-4之一伸烷氧基基團(-(CH₂)_m-O-，m係1至4之整數)、C₂-₆之一伸烯基基團(-(CH=CH)_m-，m係1至3之整數)、,C_2-6之一伸烷(氧)基羰基基團(-(R_f)_o-(C=O)-(R'_f)_p-，o及p每一者獨立地係0至2之整數且不會同時為0，且R_f及R'_f每一者獨立地係C_1-5之一烴基團或其一衍生物)、C_2-5之一羰氧基基團(-(R_g)_r-(C=O)-O-，r係0至2之整數，且R_g係C_1-4之一烴基團或其一衍生物)，及C_2-6之一環狀羰氧基基團(-(CH₂)_s-(C=O)-O-(CH₂)_t-，s及t每一者獨立地係0至3之整數，且s及t之總合係1至5)之至少一者之一個二價原子基團。 In chemical formula (1), X is an unsaturated hydrocarbon group or a derivative thereof; and each of Ra and Rb is independently a C _1-5 alkylene group (-(CH ₂ ) _m -, m is an integer of 1 to 5), an alkeneoxy group of C _1-4 (-(CH ₂ ) _m -O-, m is an integer of 1 to 4), an alkenyl group of C ₂ - ₆ (- (CH=CH) _m -, m is an integer from 1 to 3), , C _2-6 an alkylene (oxy) group carbonyl group (-(R _f ) _o -(C=O)-(R' _f ) _p- , o and p are each independently an integer from 0 to 2 and not simultaneously 0, and each of _Rf and _R'f is independently a _C1-5 hydrocarbon group or a derivative thereof compound), a carbonyloxy group of C _2-5 (-(R _g ) _r -(C=O)-O-, r is an integer from 0 to 2, and R _g is a hydrocarbon group of C _1-4 group or a derivative thereof), and a C _2-6 cyclic carbonyloxy group (-(CH ₂ ) _s -(C=O)-O-(CH ₂ ) _t -, each of s and t are independently an integer from 0 to 3, and the sum of s and t is a divalent atomic group of at least one of 1 to 5).

於Ra及Rb之每一者的碳原子數之範圍內及於Ra及Rb之每一者的p值與q值之範圍內，以化學式(1)表示之化合物之至少一者與具有親水性之水凝膠交聯聚合物具有改良反應性。相反地，當Ra及Rb之每一者的碳原子數增加或p值及n值增加，疏水性增加，且因此化合物滲入親水性水凝膠交聯聚合物之深度會改變。因為以化學式(1)表示之化合物之至少一者會於此化合物滲入水凝膠交聯聚合物之深度處反應，當以化學式(1)表示之化合物的至少一者之疏水性增加，反應實質上僅於水凝膠交聯聚合物之表面上發生，超吸收聚合物之可萃取份量(EC)及殘餘單體(RM)不會被有效降低。因此，較佳係Ra之碳原子數，Rb之碳原子數，及p值與q值係個別於上述範圍內。 Within the range of the number of carbon atoms of each of Ra and Rb and within the range of the p value and the q value of each of Ra and Rb, at least one of the compounds represented by the chemical formula (1) has a hydrophilic property. The hydrogel cross-linked polymer has improved reactivity. Conversely, as the carbon number of each of Ra and Rb increases or the p and n values increase, the hydrophobicity increases, and thus the depth of penetration of the compound into the hydrophilic hydrogel cross-linked polymer changes. Since at least one of the compounds represented by the chemical formula (1) will react at the depth where the compound penetrates into the hydrogel cross-linked polymer, when the hydrophobicity of at least one of the compounds represented by the chemical formula (1) increases, the reaction is substantially The uptake occurs only on the surface of the hydrogel cross-linked polymer, and the extractable fraction (EC) and residual monomer (RM) of the superabsorbent polymer are not effectively reduced. Therefore, it is preferable that the number of carbon atoms of Ra, the number of carbon atoms of Rb, and the p value and the q value are individually within the above-mentioned ranges.

於化學式(1)，p係2至10之整數，q係0至10之整數，且Y係一氫原子或一親水性基團。親水性基團可藉由與未反應單體及線性聚合物鏈反應形成一氫鍵，且例如，可為一羥基基團(-OH)、一羧基基團(-COOH)，及一胺基基團(-NHR_h、-NH₂，或-NR_h2，R_h係C_1-5之一烴基團)之任一者。特別地，Y係氫或羥基基團。 In chemical formula (1), p is an integer of 2 to 10, q is an integer of 0 to 10, and Y is a hydrogen atom or a hydrophilic group. Hydrophilic groups can form a hydrogen bond by reacting with unreacted monomers and linear polymer chains, and, for example, can be a hydroxyl group (-OH), a carboxyl group (-COOH), and an amine group Any of the groups (-NHR _h , -NH ₂ , or -NR _{h 2} , where _Rh is one of C _1-5 hydrocarbon groups). In particular, Y is a hydrogen or hydroxyl group.

X係C_2-5之一(甲基)乙烯基基團(CH₂=CR_a-，R_a係一氫原子，或C_1-3之一烴基團，或其一衍生物)、C_3-5之一(甲基)烯丙基基團(CH₂=CR_b-CH₂-，R_b係一氫原子，或C_1-2之一烴基團，或其一衍生物)、C_1-5之一醯基基團(R_cC(=O)-，R_c係一氫原子，或C_1-4之一烴基團，或其一衍生物)、C_3-5之一(甲基)丙烯醯基基團(CH₂=CR_d-C(=O)-，R_d係一氫原子，或 C_1-2之一烴基團，或其一衍生物)，及C_3-5之一(甲基)丙烯醯氧基基團(CH₂=CR_e-C(=O)-O-，R_e係一氫原子，或C_1-2之一烴基團，或其一衍生物)之至少一者的一單價原子基團。特別地，X可為C_3-5之一(甲基)丙烯醯基基團(CH₂=CR_d-C(=O)-，R_d係一氫原子，或C_1-2之一烴基團，或其一衍生物)。 X is a (methyl) vinyl group of C _2-5 (CH ₂ =CR _a -, R _a is a hydrogen atom, or a hydrocarbon group of C _1-3 , or a derivative thereof), C ₃ One of _-5 (meth)allyl group (CH ₂ =CR _b -CH ₂ -, R _b is a hydrogen atom, or one of C _1-2 hydrocarbon groups, or a derivative thereof), C ₁ One of _-5 acyl group (R _c C(=O)-, R _c is a hydrogen atom, or one of C _1-4 hydrocarbon group, or one of its derivatives), one of C _3-5 (methyl group) acryl group (CH ₂ =CR _d -C(=O)-, R _d is a hydrogen atom, or a hydrocarbon group of C _1-2 , or a derivative thereof), and C _3-5 One (meth)acryloyloxy group (CH ₂ =CR _e -C(=O)-O-, R _e is a hydrogen atom, or one of C _1-2 hydrocarbon groups, or a derivative thereof ) is a monovalent atomic group of at least one of . In particular, X can be one of C _3-5 (meth)acryloyl groups (CH ₂ =CR _d -C(=O)-, R _d is a hydrogen atom, or one of C _1-2 hydrocarbyl groups group, or a derivative thereof).

相對於超吸收聚合物之總含量，以化學式(1)表示之化合物之至少一者的含量可於多於0.1重量%到少於10重量%之範圍。當其含量於上述範圍內，超吸收聚合物之物理性質可被改良。例如，超吸收聚合物之離心滯留能力(CRC)降低可最小化。 The content of at least one of the compounds represented by the chemical formula (1) may range from more than 0.1 wt % to less than 10 wt % with respect to the total content of the superabsorbent polymer. When its content is within the above range, the physical properties of the superabsorbent polymer can be improved. For example, the centrifugal retention capacity (CRC) reduction of the superabsorbent polymer can be minimized.

以化學式(1)表示之化合物的至少一者可為以如下化學式(2)表示之化合物的至少一者。 At least one of the compounds represented by the chemical formula (1) may be at least one of the compounds represented by the following chemical formula (2).

於化學式(2)，R₁可為C_1-2之一烷基基團及C_1-2之一烷氧基基團之任一者；R₂可為C_1-5之一伸烷基基團(-(CH₂)_m-，m係1至5之整數)、C_1-5之一伸烷氧基基團(-(CH₂)_m-O-，m係1至5之整數)，及C_2-6之一環狀羰氧基基團(-(CH₂)_s-(C=O)-O-(CH₂)_t-，s及t每一者獨立地係0至3之整 數，且s及t之總合係1至5)之任一者；Y可為一氫及羥基基團(-OH)之任一者；且n係1至10之整數。 In chemical formula (2), R ₁ can be any one of an alkyl group of C _1-2 and an alkoxy group of C _1-2 ; R ₂ can be an alkylene group of C _1-5 group (-(CH ₂ ) _m -, m is an integer of 1 to 5), an alkoxy group of C _1-5 (-(CH ₂ ) _m -O-, m is an integer of 1 to 5), and a cyclic carbonyloxy group of C _2-6 (-(CH ₂ ) _s -(C=O)-O-(CH ₂ ) _t -, each of s and t is independently one of 0 to 3 An integer, and the sum of s and t is any of 1 to 5); Y can be any one of a hydrogen and a hydroxyl group (-OH); and n is an integer of 1 to 10.

以化學式(2)表示之化合物的至少一者可為以化學式(3)至(22)表示之化合物的至少一者。 At least one of the compounds represented by the chemical formula (2) may be at least one of the compounds represented by the chemical formulas (3) to (22).

<化學式(9)>

<Chemical formula (9)>

<化學式(12)>

<Chemical formula (12)>

<化學式(15)>

<Chemical formula (15)>

<化學式(19)>

<Chemical formula (19)>

於使經表面處理之基底樹脂乾燥之步驟(P62)， 此經表面處理之基底樹脂可於約150℃至約200℃之溫度熱處理約20分鐘至約60分鐘。 In the step of drying the surface-treated base resin (P62), The surface-treated base resin may be heat-treated at a temperature of about 150°C to about 200°C for about 20 minutes to about 60 minutes.

其後，會參考下例範例及實驗例詳細說明依據本發明之一種製備超吸收聚合物之方法可提供含有小量的水溶性組份及殘餘單體且具有改良的離心滯留能力之一超吸收聚合物。 Afterwards, a method for preparing a superabsorbent polymer according to the present invention will be described in detail with reference to the following examples and experimental examples, which can provide a superabsorbent with a small amount of water-soluble components and residual monomers with improved centrifugal retention capacity. polymer.

<比較例1> <Comparative Example 1>

500克之丙烯酸與971.4克之20%氫氧化鈉水溶液混合，然後，添加1.5克之作為一內部交聯劑之乙氧基-三羥甲基丙烷三丙烯酸酯及0.165克之作為一光聚合反應起始劑之二苯基(2,4,5-三甲基苯甲醯基)-膦氧化物，以便製備一水溶性不飽和單體溶液(以丙烯酸為主之單體的聚合反應度：70莫耳%)。 500 g of acrylic acid was mixed with 971.4 g of 20% aqueous sodium hydroxide solution, and then, 1.5 g of ethoxy-trimethylolpropane triacrylate as an internal crosslinking agent and 0.165 g of ethoxy-trimethylolpropane triacrylate as a photopolymerization initiator were added. Diphenyl(2,4,5-trimethylbenzyl)-phosphine oxide in order to prepare a water-soluble unsaturated monomer solution (polymerization degree of acrylic acid-based monomer: 70 mol% ).

一單體混合物之光聚合反應係藉由紫外線照射實施，以便製備一細微水凝膠聚合物。 Photopolymerization of a monomer mixture is carried out by UV irradiation to prepare a fine hydrogel polymer.

製備之水凝膠聚合物經由一碎肉機製成水凝膠聚合物顆粒，然後，藉由一熱空氣帶式乾燥器於170℃乾燥40分鐘。經乾燥之水凝膠聚合物藉由一切割研磨粉碎機粉碎，然後過篩，以便獲得具有約150μm至約850μm之平均顆粒尺寸的一基底聚合物。 The prepared hydrogel polymer was formed into hydrogel polymer particles by a meat chopper, and then dried by a hot air belt dryer at 170° C. for 40 minutes. The dried hydrogel polymer is pulverized by a cutting mill pulverizer and then sieved to obtain a base polymer having an average particle size of about 150 μm to about 850 μm.

其後，100克之獲得的基底聚合物與含有1克之伸乙基碳酸酯，3克之水，及3克之乙醇的一表面交聯溶液混合，然後，一反應於180℃之一熱烘箱中實施30分鐘。反應產物被過篩，以便製備具有約150μm至約850μm之顆粒尺 寸的一經表面處理之聚合物。 Thereafter, 100 g of the obtained base polymer was mixed with a surface crosslinking solution containing 1 g of ethyl acetate, 3 g of water, and 3 g of ethanol, and then, a reaction was carried out in a hot oven at 180° C. for 30 minute. The reaction product is sieved to prepare a particle size of about 150 μm to about 850 μm inch of surface-treated polymer.

<範例1> <Example 1>

除了使0.5克之具有6莫耳之環氧乙烷單位之聚乙二醇單甲基丙烯酸酯(Bisomer PEM 6LD，6 EO單位，製造商：Cognis)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 Except that 0.5 g of polyethylene glycol monomethacrylate having 6 moles of ethylene oxide units (Bisomer PEM 6LD, 6 EO units, manufacturer: Cognis) was added to the surface crosslinking solution, once the surface treatment The superabsorbent polymer was prepared in the same manner as in Comparative Example 1.

<範例2> <Example 2>

除了使1克之具有6莫耳之環氧乙烷單位之聚乙二醇單甲基丙烯酸酯(Bisomer PEM 6LD，6 EO單位，製造商：Cognis)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 Except that 1 gram of polyethylene glycol monomethacrylate having 6 moles of ethylene oxide units (Bisomer PEM 6LD, 6 EO units, manufacturer: Cognis) was added to the surface crosslinking solution, once the surface treatment The superabsorbent polymer was prepared in the same manner as in Comparative Example 1.

<範例3> <Example 3>

除了使2克之具有6莫耳之環氧乙烷單位之聚乙二醇單甲基丙烯酸酯(Bisomer PEM 6LD，6 EO單位，製造商：Cognis)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 Except that 2 g of polyethylene glycol monomethacrylate with 6 moles of ethylene oxide units (Bisomer PEM 6LD, 6 EO units, manufacturer: Cognis) was added to the surface crosslinking solution, once the surface treatment The superabsorbent polymer was prepared in the same manner as in Comparative Example 1.

<範例4> <Example 4>

除了使0.5克之聚(乙二醇)甲基丙烯酸酯(平均Mn 500，製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 0.5 g of poly(ethylene glycol) methacrylate (average Mn 500, manufacturer: aldrich) was added to the surface crosslinking solution .

<範例5> <Example 5>

除了使1克之聚(乙二醇)甲基丙烯酸酯(平均Mn 500，製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 1 gram of poly(ethylene glycol) methacrylate (average Mn 500, manufacturer: aldrich) was added to the surface crosslinking solution .

<範例6> <Example 6>

除了使2克之聚(乙二醇)甲基丙烯酸酯(平均Mn 500，製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 2 g of poly(ethylene glycol) methacrylate (average Mn 500, manufacturer: aldrich) was added to the surface crosslinking solution .

<範例7> <Example 7>

除了使0.5克之丙烯酸2-羥基乙酯(製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 0.5 g of 2-hydroxyethyl acrylate (manufacturer: aldrich) was added to the surface crosslinking solution.

<範例8> <Example 8>

除了使1克之丙烯酸2-羥基乙酯(製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 1 gram of 2-hydroxyethyl acrylate (manufacturer: aldrich) was added to the surface crosslinking solution.

<範例9> <Example 9>

除了使2克之丙烯酸2-羥基乙酯(製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 2 g of 2-hydroxyethyl acrylate (manufacturer: aldrich) was added to the surface crosslinking solution.

<範例10> <Example 10>

除了使0.5克之丙烯酸羥基丙酯(異構物混合物，製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 0.5 g of hydroxypropyl acrylate (mixture of isomers, manufacturer: aldrich) was added to the surface crosslinking solution.

<範例11> <Example 11>

除了使1克之丙烯酸羥基丙酯(異構物混合物，製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 1 gram of hydroxypropyl acrylate (mixture of isomers, manufacturer: aldrich) was added to the surface crosslinking solution.

<範例12> <Example 12>

除了使2克之丙烯酸羥基丙酯(異構物混合物，製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 2 g of hydroxypropyl acrylate (mixture of isomers, manufacturer: aldrich) was added to the surface crosslinking solution.

<範例13> <Example 13>

除了使0.5克之甲基丙烯酸2-羥基乙酯(製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 0.5 g of 2-hydroxyethyl methacrylate (manufacturer: aldrich) was added to the surface crosslinking solution.

<範例14> <Example 14>

除了使1克之甲基丙烯酸2-羥基乙酯(製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 1 gram of 2-hydroxyethyl methacrylate (manufacturer: aldrich) was added to the surface crosslinking solution.

<範例15> <Example 15>

除了使2克之甲基丙烯酸2-羥基乙酯(製造商：aldrich)添加至表面交聯溶液外，一經表面處理之超吸收聚合物係以與比較例1相同之方式製備。 A surface-treated superabsorbent polymer was prepared in the same manner as Comparative Example 1, except that 2 g of 2-hydroxyethyl methacrylate (manufacturer: aldrich) was added to the surface crosslinking solution.

<實驗例1> <Experimental example 1>

比較例1及範例1至15獲得之超吸收聚合物的每一者之粉末的離心滯留能力(CRC)、可萃取份量(EC)、於加壓下之吸收率(AUP)，及殘餘單體(RM)被個別測得，且其結果綜述於表之表1中。below.The analyses of the其離心滯留能力(CRC)、於加壓下之吸收率(AUP)、可萃取份量(EC)，及殘餘單體(RM)之分析係依據EDANA(歐洲拋棄物及不織布協會(European Disposables and Nonwovens Association))WSP241.2.R3、EDANA WSP242.2.R3、EDANA WSP270.2.R3，及EDANA WSP 210.2.R3個別實施。 Centrifugal Retention Capacity (CRC), Extractable Part (EC), Absorbance Under Pressure (AUP), and Residual Monomer of the powders of each of the superabsorbent polymers obtained in Comparative Example 1 and Examples 1 to 15 (RM) was measured individually and the results are summarized in Table 1 of the Tables. Below. The analyses of the Centrifugal Retention Capacity (CRC), Absorption Under Pressure (AUP), Extractable Content (EC), and Residual Monomer (RM) are based on EDANA (European Discards and Nonwovens) Association (European Disposables and Nonwovens Association)) WSP241.2.R3, EDANA WSP242.2.R3, EDANA WSP270.2.R3, and EDANA WSP 210.2.R3 are implemented individually.

參考表1，可確認範例1及2之超吸收聚合物(此等係藉由使以上述化學式(1)表示之化合物添加至一表面交聯溶液而製備)的每一者之可萃取份量(EC)及殘餘單體(RM)濃度係低於未添加此化合物的比較例1之超吸收聚合物者。再者，可確認其降低可萃取份量(EC)及殘餘單體(RM)濃度之功效係依此化合物含量之增加而增加。 Referring to Table 1, it was possible to confirm the extractable amount ( EC) and residual monomer (RM) concentrations were lower than those of the superabsorbent polymer of Comparative Example 1 to which this compound was not added. Furthermore, it can be confirmed that its efficacy in reducing extractable fraction (EC) and residual monomer (RM) concentration increases with increasing content of this compound.

於總結詳細說明，熟習此項技藝者會瞭解許多變化及修改可於實質上偏離本發明原則下對較佳實施例進 行。因此，本發明之揭露較佳實施例係僅以一般性及描述性且非限制性目的而使用。 In concluding the detailed description, those skilled in the art will appreciate that many variations and modifications can be made to the preferred embodiment without substantially departing from the principles of this invention. OK. Accordingly, the disclosed preferred embodiments of the present invention are presented for general and descriptive, and non-limiting purposes only.

P1‧‧‧製備單體組成物 P1‧‧‧Preparation of monomer composition

P11‧‧‧製備包括親水性單體及中和劑之第一組成物 P11‧‧‧Preparation of first composition including hydrophilic monomer and neutralizing agent

P12‧‧‧藉由使第一組成物與交聯劑及聚合反應起始劑混合製備第二組成物 P12‧‧‧Preparation of the second composition by mixing the first composition with the crosslinking agent and the polymerization initiator

P2‧‧‧製備水凝膠交聯聚合物 P2‧‧‧Preparation of hydrogel cross-linked polymer

P3‧‧‧使水凝膠交聯聚合物粉碎 P3‧‧‧Pulverize the hydrogel cross-linked polymer

P4‧‧‧使經粉碎之水凝膠交聯聚合物乾燥 P4‧‧‧Drying the crushed hydrogel cross-linked polymer

P5‧‧‧藉由使經乾燥之水凝膠交聯聚合物粉碎製備基底樹脂 P5‧‧‧Preparation of base resin by pulverizing dried hydrogel cross-linked polymer

P6‧‧‧使基底樹脂表面交聯 P6‧‧‧Crosslinking the surface of the base resin

P61‧‧‧使基底樹脂與以如下化學式(1)表示之化合物之至少一者及表面交聯劑混合X-(Ra)_p(Rb)_q-Y----(1) P61‧‧‧Mix the base resin with at least one of the compounds represented by the following chemical formula (1) and a surface crosslinking agent X-(Ra) _p (Rb) _q -Y----(1)

P62‧‧‧使經表面處理之基底樹脂乾燥 P62‧‧‧Dry the surface-treated base resin

Claims (9)

一種製備超吸收聚合物之方法，包含步驟：藉由使包括親水性單體、一交聯劑，及一聚合反應起始劑之一單體組成物聚合製備一水凝膠交聯聚合物；使該水凝膠交聯聚合物粉碎；使該經粉碎之水凝膠交聯聚合物乾燥；藉由使該經乾燥之水凝膠交聯聚合物粉碎製備一基底樹脂；及使該基底樹脂與以如下化學式(1)表示之一化合物及一表面交聯劑混合使該基底樹脂表面交聯：X-(Ra)_p(Rb)_q-Y----(1)於該化學式(1)，X係一不飽和烴基團或其一衍生物；Ra及Rb每一者獨立地係C_1-5之一伸烷基基團(-(CH₂)_m-，m係1至5整數)、C_1-4之一伸烷氧基基團(-(CH₂)_m-O-，m係1至4之整數)、C_2-6之一伸烯基基團(-(CH=CH)_m-，m係1至3之整數)、C_2-6之一伸烷(氧)基羰基基團(-(R_f)_o-(C=O)-(R'_f)_p-，o及p每一者獨立地係0至2之整數且不會同時為0，且R_f及R'_f每一者獨立地係C_1-5之一烴基團，或其一衍生物)、C_2-5之一羰氧基基團(-(R_g)_r-(C=O)-O-，r係0至2之整數，且R_g係C_1-4之一烴基團，或其一衍生物)，及C_2-6之一環狀羰氧基基團(-(CH₂)_s-(C=O)-O-(CH₂)_t-，s及t每一者獨立地係0至3之整數，且s及t之總合係1至5)之至少一者之一個二價原子基 團；p係2至10之整數；q係0至10之整數；且Y係一氫原子或一親水性基團；以及其中，X係C_2-5之一(甲基)乙烯基基團(CH₂=CR_a-，R_a係一氫原子，或C_1-3之一烴基團，或其一衍生物)、C_3-5之一(甲基)烯丙基基團(CH₂=CR_b-CH₂-，R_b係一氫原子，或C_1-2之一烴基團，或其一衍生物)、C_1-5之一醯基基團(R_cC(=O)-，R_c係一氫原子，或C_1-4之一烴基團，或其一衍生物)、C_3-5之一(甲基)丙烯醯基基團(CH₂=CR_d-C(=O)-，R_d係一氫原子，或C_1-2之一烴基團，或其一衍生物)，及C_3-5之一(甲基)丙烯醯氧基基團(CH₂=CR_e-C(=O)-O-，R_e係一氫原子，或C_1-2之一烴基團，或其一衍生物)之至少一者之一單價原子基團；其中，該表面交聯劑是選自由下列組成之群組中的至少一化合物：烷基二元醇類、伸烷基二醇類、烷基二縮水甘油醚類、多價金屬類、乙二醇二縮水甘油醚類、伸烷基碳酸酯類、水及乙醇。 A method for preparing a superabsorbent polymer, comprising the steps of: preparing a hydrogel cross-linked polymer by polymerizing a monomer composition comprising a hydrophilic monomer, a cross-linking agent, and a polymerization initiator; pulverizing the hydrogel cross-linked polymer; drying the pulverized hydrogel cross-linked polymer; preparing a base resin by pulverizing the dried hydrogel cross-linked polymer; and making the base resin Mixing with a compound represented by the following chemical formula (1) and a surface crosslinking agent to crosslink the surface of the base resin: X-(Ra) _p (Rb) _q -Y----(1) in the chemical formula (1) ), X is an unsaturated hydrocarbon group or a derivative thereof; Ra and Rb are each independently a C _1-5 alkylene group (-(CH ₂ ) _m -, m is an integer from 1 to 5) , C _1-4 alkaneoxy group (-(CH ₂ ) _m -O-, m is an integer from 1 to 4), C _2-6 alkene group (-(CH=CH) _m -, m is an integer from 1 to 3), an alkane(oxy)yl carbonyl group of C _2-6 (-(R _f ) _o -(C=O)-(R' _f ) _p -, o and p each independently is an integer from 0 to 2 and not simultaneously 0, and each of _Rf and _R'f is independently a hydrocarbon group of _C1-5 , or a derivative thereof), _C2- A carbonyloxy group of ₅ (-(R _g ) _r -(C=O)-O-, r is an integer from 0 to 2, and R _g is a hydrocarbon group of C _1-4 , or a derivative thereof compound), and a cyclic carbonyloxy group of _C2-6 (-( _CH2 ) _s- (C=O)-O-( _CH2 ) _t- , each of s and t is independently 0 an integer from 3 to 3, and the sum of s and t is a divalent atomic group of at least one of 1 to 5); p is an integer from 2 to 10; q is an integer from 0 to 10; and Y is a hydrogen atom or a hydrophilic group; and wherein, X is a (methyl) vinyl group of C _2-5 (CH ₂ =CR _a -, R _a is a hydrogen atom, or a hydrocarbon group of C _1-3 group, or a derivative thereof), one of C _3-5 (methyl) allyl group (CH ₂ =CR _b -CH ₂ -, R _b is a hydrogen atom, or one of C _1-2 hydrocarbon group group, or a derivative thereof), an acyl group of C _1-5 (R _c C(=O)-, R _c is a hydrogen atom, or a hydrocarbon group of C _1-4 , or a derivative thereof compound), one of C _3-5 (meth)acryloyl group (CH ₂ =CR _d -C(=O)-, R _d is a hydrogen atom, or one of C _1-2 hydrocarbon group, or one of its derivatives), and one of C _3-5 (meth)acryloyloxy groups (CH ₂ =CR _e -C(=O)-O-, R _e is a hydrogen atom, or C _{1- 2} , a hydrocarbon group, or a monovalent atom group of at least one of a derivative thereof); wherein, the surface cross-linking agent is at least one compound selected from the group consisting of: alkyl di Alcohols, alkylene glycols, alkyl diglycidyl ethers, polyvalent metals, ethylene glycol diglycidyl ethers, alkylene carbonates, water and ethanol. 如請求項1之方法，其中，該親水性基團係一羥基基團(-OH)、一羧基基團(-COOH)，及一胺基基團(-NHR_h、-NH₂，或-NR_h2，R_h係C_1-5之一烴基團)之任一者。 The method of claim 1, wherein the hydrophilic group is a hydroxyl group (-OH), a carboxyl group (-COOH), and an amine group (-NHR _h , -NH ₂ , or - NR _h2 , _Rh is any one of C _1-5 hydrocarbon groups). 如請求項1之方法，其中，X係C_3-5之一(甲基)丙烯醯基基團(CH₂=CR_d-C(=O)-，R_d係一氫原子，或C_1-2之一烴基團，或其一衍生物)，且Y係一氫原子或一羥基基團。 The method of claim 1, wherein X is a (meth)acryloyl group of C _3-5 (CH ₂ =CR _d -C(=O)-, R _d is a hydrogen atom, or C _{1 -2} is a hydrocarbon group, or a derivative thereof), and Y is a hydrogen atom or a hydroxyl group. 如請求項1之方法，其中，以該化學式(1)表示之該等化合物之至少一者係以如下化學式(2)表示之化合物之至 少一者：

於該化學式(2)，R₁係C_1-2之一烷基基團及C_1-2之一烷氧基基團之任一者；R₂係C_1-5之一伸烷基基團(-(CH₂)_m-，m係1至5)、C_1-5之一伸烷氧基基團(-(CH₂)_m-O-，m係1至5之整數)，及C_2-6之一環狀羰氧基基團(-(CH₂)_s-(C=O)-O-(CH₂)_t-，s及t每一者獨立地係0至3之整數，且s及t之總合係1至5)之任一者；Y係一氫原子及一羥基基團(-OH)之任一者；且n係1至10之整數。 The method of claim 1, wherein at least one of the compounds represented by the chemical formula (1) is at least one of the compounds represented by the following chemical formula (2):

In the chemical formula (2), R ₁ is any one of an alkyl group of C _1-2 and an alkoxy group of C _1-2 ; R ₂ is an alkylene group of C _1-5 (-(CH ₂ ) _m -, m is 1 to 5), an alkoxy group of C _1-5 (-(CH ₂ ) _m -O-, m is an integer of 1 to 5), and C _{2 -6} A cyclic carbonyloxy group (-( _CH2 ) _s- (C=O)-O-( _CH2 ) _t- , each of s and t is independently an integer from 0 to 3, and The sum of s and t is any one of 1 to 5); Y is any one of a hydrogen atom and a hydroxyl group (—OH); and n is an integer of 1 to 10. 如請求項4之方法，其中，以該化學式(2)表示之該等化合物之至少一者係以化學式(3)至(22)表示之化合物之至少一者：

The method of claim 4, wherein at least one of the compounds represented by the chemical formula (2) is at least one of the compounds represented by the chemical formulas (3) to (22):

如請求項1之方法，進一步包含：製備該單體組成物，其中，該製備該單體組成物包括：製備包括該等親水性單體及一中和劑之一第一組成物；藉由使該第一組成物與該交聯劑及該聚合反應起始劑混合製備一第二組成物。 The method of claim 1, further comprising: preparing the monomer composition, wherein the preparing the monomer composition comprises: preparing a first composition comprising the hydrophilic monomers and a neutralizing agent; by The first composition is mixed with the cross-linking agent and the polymerization initiator to prepare a second composition. 如請求項1之方法，其中，該聚合反應起始劑係一光聚合反應起始劑、一熱聚合反應起始劑，及一氧化還原起始劑之至少一者。 The method of claim 1, wherein the polymerization initiator is at least one of a photopolymerization initiator, a thermal polymerization initiator, and a redox initiator. 如請求項1之方法，其中，該使該基底樹脂表面交聯進一步包括：使該經表面處理之基底樹脂乾燥。 The method of claim 1, wherein the surface-crosslinking of the base resin further comprises: drying the surface-treated base resin. 如請求項1之方法，其中，該伸烷基碳酸酯類是伸乙基碳酸酯。 The method of claim 1, wherein the alkylene carbonates are ethylidene carbonates.

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