TW202136328A - 聚乙烯醇系樹脂、聚乙烯醇系樹脂之製造方法、分散劑以及懸浮聚合用分散劑 - Google Patents
聚乙烯醇系樹脂、聚乙烯醇系樹脂之製造方法、分散劑以及懸浮聚合用分散劑 Download PDFInfo
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- TW202136328A TW202136328A TW110101584A TW110101584A TW202136328A TW 202136328 A TW202136328 A TW 202136328A TW 110101584 A TW110101584 A TW 110101584A TW 110101584 A TW110101584 A TW 110101584A TW 202136328 A TW202136328 A TW 202136328A
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- Prior art keywords
- pva
- based resin
- polyvinyl alcohol
- polymerization
- vinyl
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- 239000011347 resin Substances 0.000 title claims abstract description 167
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 149
- 239000002270 dispersing agent Substances 0.000 title claims description 38
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- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000002835 absorbance Methods 0.000 claims abstract description 26
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
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- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- OIIWPAYIXDCDNL-HGFPCDIYSA-M sodium;2,2,3,3-tetradeuterio-3-trimethylsilylpropanoate Chemical compound [Na+].[O-]C(=O)C([2H])([2H])C([2H])([2H])[Si](C)(C)C OIIWPAYIXDCDNL-HGFPCDIYSA-M 0.000 description 1
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- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—Vinyl acetate
-
- 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
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
-
- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/34—Higher-molecular-weight carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/52—Natural or synthetic resins or their salts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本發明係關於聚乙烯醇系樹脂,其嵌段特徵值(A)小於0.4,將該聚乙烯醇系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)為0.2以上。
Description
本發明係關於聚乙烯醇系樹脂,更詳言之,係關於適於作為在聚氯乙烯製造時將乙烯基系化合物予以懸浮聚合時使用之分散劑的聚乙烯醇系樹脂、聚乙烯醇系樹脂之製造方法、分散劑、以及懸浮聚合用分散劑。
聚乙烯醇系樹脂(以下有時「聚乙烯醇」簡稱「PVA」),係將乙酸乙烯酯等乙烯酯系單體聚合而得的聚合物予以皂化而獲得,具有相應皂化度之乙烯醇結構單元以及未皂化而殘留的乙烯酯結構單元。進一步將PVA系樹脂進行熱處理,會使其脫水及脫乙酸,會成為在主鏈中帶有雙鍵之結構,具有該結構之PVA系樹脂使用於聚氯乙烯製造時之懸浮用分散安定劑、保水材等用途。又,也已知藉由對於使用PVA系樹脂而成之薄膜、纖維進行熱處理,能夠使強度更好。
另一方面,針對製造聚氯乙烯時之懸浮聚合用分散劑已有人探討各種熱處理PVA系樹脂。例如有人提案分子內具有羰基且含有2~3價之金屬之鹽或氫氧化物之聚乙烯醇系樹脂(例如參照專利文獻1)。又,有人提案一種PVA系聚合物,其濃度0.1重量%水溶液之紫外吸收光譜測得之280nm之吸光度(a)大於0.1,該水溶液之紫外吸收光譜測得之320nm之吸光度(b)為0.03以上,且吸光度(b)/吸光度(a)小於0.3,且殘存乙酸基之嵌段特徵值(block character)為0.4以上(例如參照專利文獻2)。
PVA系樹脂中之雙鍵在氯乙烯單體懸浮聚合時係吸附在氯乙烯單體、接續作為接枝反應之起點作用,故一般已知該雙鍵越多則聚合安定性越優良。
但是為了獲得有雙鍵之PVA系樹脂,如專利文獻1及2所記載,需於約150℃進行5~6小時熱處理,會有製造成本提高的問題。
為了解決上述課題,有人提案使用雙軸擠壓機來實施熱處理(例如:專利文獻3)。專利文獻3記載之PVA系樹脂係分子內有羰基且殘存脂肪酸酯基之嵌段特徵值(block character)為0.5以上之聚乙烯醇系樹脂,聚乙烯醇樹脂之0.1重量%水溶液之紫外線吸收光譜測得之215nm、280nm、320nm之吸光度各為0.1以上,且320nm之吸光度/280nm之吸光度之比為0.3以上。
[先前技術文獻]
[專利文獻]
專利文獻1:日本特開平08-269112號公報
專利文獻2:日本特開平08-283313號公報
專利文獻3:日本特開2004-250695號公報
(發明欲解決之課題)
但是上述PVA系樹脂係為了使聚合安定性更好而實行了強力熱處理而獲得者。經強力熱處理之PVA系樹脂,因獲得之PVA系樹脂之嵌段特徵值提高因而分散性降低,使用上述PVA系樹脂作為懸浮聚合用分散劑時,會有不易獲得多孔質性之氯乙烯樹脂的問題。
本發明的課題為提供為了提高懸浮聚合物(例如:聚氯乙烯)聚合時之聚合安定性而樹脂中之雙鍵之含量多並且分散性優異之PVA系樹脂、及使用了該PVA系樹脂之分散劑及聚氯乙烯製造時使用之懸浮聚合用分散劑。
(解決課題之方式)
本案發明人等為了解決上述課題而努力研究,結果發現獲得樹脂中之雙鍵之含量多而嵌段特徵值之值小之PVA系樹脂,乃完成本發明。
亦即本發明係關於下列[1]~[5]。
[1] 一種聚乙烯醇系樹脂,其嵌段特徵值(A)小於0.4,且該聚乙烯醇系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)為0.2以上。
[2] 如[1]之聚乙烯醇系樹脂,其中,該聚乙烯醇系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)相對於該嵌段特徵值(A)之比(B/A)為0.6以上。
[3] 一種分散劑,係由如[1]或[2]之聚乙烯醇系樹脂構成。
[4] 一種懸浮聚合用分散劑,係由如[1]或[2]之聚乙烯醇系樹脂構成。
[5] 一種如[1]或[2]之聚乙烯醇系樹脂之製造方法,包括邊導入含氧氣體邊將含乙烯酯系單體之單體組成物進行聚合而獲得乙烯酯系聚合物之步驟。
依照本發明,可獲得樹脂中之雙鍵之含量多而嵌段特徵值之值小的PVA系樹脂。故使用該PVA系樹脂作為懸浮聚合用分散劑時,推測能使懸浮聚合物(例如:聚氯乙烯)之聚合安定性更好,也能使分散安定性也更好。
以下針對本發明之聚乙烯醇系樹脂詳細說明,但此等係理想實施態樣之一例,並非限於該等內容。本說明書中,重量基準之比例(百分率、份等),係同於質量基準之比例(百分率、份等)。
[聚乙烯醇系樹脂]
本發明之聚乙烯醇系樹脂(以下稱為PVA系樹脂),嵌段特徵值(A)小於0.4,且前述聚乙烯醇系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)為0.2以上。
本發明之PVA系樹脂,嵌段特徵值(A)小於0.4,較佳為0.25以上且小於0.4,更佳為0.3以上且小於0.4,更佳為0.35以上且小於0.4。嵌段特徵值(A)藉由小於0.4,PVA系樹脂之分散安定能力提高。前述嵌段特徵值(A)之值若過大,則使用PVA系樹脂作為懸浮聚合用分散劑時,會有懸浮聚合獲得之乙烯基系樹脂之塑化劑吸收性降低、或粒度分布變廣之傾向,(A)之值若過小會有聚合安定性變差的傾向。
該嵌段特徵值(A),係從使用3-(三甲基矽基)-2,2,3,3-d4
-丙酸鈉鹽(3-(trimethylsilyl)propionic-2,2,3,3-d4
acid sodium salt)作為內部標準物質之13
C-NMR測定中,於38~49ppm之範圍觀察到的基於亞甲基碳部分之吸收[(OH,OH)dyad之吸收=43.5~46ppm、(OH,OR)dyad之吸收=41.0~43.5ppm、(OR,OR)dyad之吸收=38~40.5ppm,惟R代表乙醯基(CH3
CO-)。]之吸收強度比求出,係依下式算出之值。
嵌段特徵值(A)=(OH,OR)/2(OH)(OR)
(惟(OH,OR)、(OH)、(OR)皆是按莫耳分率計算。又,(OH)係依13
C-NMR之積分比算出之皂化度(莫耳分率),例如使用乙酸乙烯酯作為脂肪酸乙烯酯時,(OR)代表此時之乙醯氧基之莫耳分率。)
嵌段特徵值係代表聚乙烯醇系樹脂中之脂肪酸酯單元之平均鏈長之程度,值越大代表殘存之脂肪酸酯嵌段之平均鏈長越短(脂肪酸酯單元之無規性高)。針對嵌段特徵值及其測定方法,詳述於PVA(發行所:高分子刊行會、1984)及Macromolecules, 10, 532(1977)。
本發明之PVA系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)為0.2以上,較佳為0.25以上,更佳為0.30以上。該吸光度(B)之值藉由為上述下限值以上,PVA系樹脂之雙鍵量容易成為充分量,PVA系樹脂作為懸浮聚合用分散劑時之聚合安定性提高。上限不特別限定,考量製造可能性之觀點,為約1.5。前述吸光度(B)之值若過小,PVA系樹脂內之雙鍵之生成少,故PVA系樹脂作為各種分散劑使用時,會有界面活性能力降低之傾向。又,前述吸光度(B)之值若過大,PVA系樹脂作為懸浮聚合用分散劑使用時,會有獲得之聚氯乙烯等平均粒徑變得過小而操作性變差的傾向。
又,本發明中,本發明之PVA系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)相對於前述嵌段特徵值(A)之比(B/A)為0.5以上較佳,更佳為0.6以上。(B/A)藉由為上述下限值以上,作為懸浮聚合用分散劑時之聚合安定性提高,故較理想。前述之比(B/A)若過小,作為氯乙烯等懸浮聚合用分散劑使用時,會有界面活性能力降低,懸浮聚合安定性降低之傾向。上限不特別限定,考量生產性之觀點,為約3。
該吸光度,係使用紫外可見近紅外分光光度計(例如:日本分光(股)公司製「V-560」(商品名))測定PVA系樹脂之0.1重量%水溶液之吸光度而獲得之值。又,吸光度係使用光路長1cm之試樣容器(光析管)測定。
一般而言,PVA系樹脂係將乙烯酯系單體之均聚物、或乙烯酯系單體與其他單體之共聚物(以下有時將它們稱為「乙烯酯系聚合物」)使用鹼觸媒等予以皂化獲得之樹脂。
本發明之PVA系樹脂之皂化度為60莫耳%以上較佳,更佳為65~98莫耳%,再更佳為67~90莫耳%,又更佳為69~88莫耳%,尤佳為70~82莫耳%。本發明之PVA系樹脂,在分子中除了羥基(親水性)尚存在乙酸基(疏水基),故有界面活性能力,能對於分散媒均勻分散。皂化度若過低則有水分散性降低之傾向,皂化度為60莫耳%以上較佳。皂化度係依據JIS K 6726:1994測定之值。
本發明之PVA系樹脂之平均聚合度為100~4000較佳,更佳為200~3000,尤佳為200~2000。平均聚合度若過低,會有界面活性能降低之傾向,作為氯乙烯懸浮聚合用分散劑使用時,懸浮聚合時易引起凝聚。反之,平均聚合度若過高,PVA系樹脂水溶液之黏度上昇,操作性容易降低。又,平均聚合度可依JIS K 6726:1994測定。
製造時,例如為了使樹脂中之雙鍵量為充分量而經熱處理之PVA系樹脂,易起黃變,使用該PVA系樹脂作為懸浮聚合用分散劑時獲得之氯乙烯等樹脂之色相有時會變差。另一方面,獲得本發明之PVA系樹脂時,即使不經熱處理,雙鍵之含量亦能相對較高,故本發明之PVA系樹脂容易有較小的YI值,黃變抑制性易良好。
[聚乙烯醇系樹脂之製造方法]
本發明之PVA系樹脂,如上述,嵌段特徵值(A)小於0.4,且前述PVA系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)為0.2以上。
首先,針對獲得嵌段特徵值(A)小於0.4且製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)為0.2以上之PVA系樹脂之方法說明。該方法例如可列舉以下之方法(i)~(iv)。
(i)於含氧條件下將含有乙烯酯系單體之單體組成物進行自由基聚合,並將獲得之乙烯酯系聚合物進行皂化反應之方法。
(ii)於氧及醛共存下,將含有乙烯酯系單體之單體組成物進行自由基聚合,並將獲得之乙烯酯系聚合物進行皂化反應之方法。
(iii)將有雙鍵之乙烯醇系樹脂進行再乙酸化,將獲得之乙烯酯系聚合物進行皂化反應之方法。
(iv)於甲醛共存下將含有乙烯酯系單體之單體組成物進行自由基聚合,並將獲得之乙烯酯系聚合物進行皂化反應之方法。
其中,考量生產性之觀點,上述(i)或(ii)的方法較佳。
以下取上述(i)的方法為例,說明本發明之PVA系樹脂之製造方法。
為起始原料之單體組成物包括乙烯酯系單體。乙烯酯系單體,例如:甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯及其他之直鏈或分支狀之飽和脂肪酸乙烯酯等。考量實用的觀點,使用乙酸乙烯酯作為乙烯酯系單體較佳,例如:乙酸乙烯酯單獨使用,或將乙酸乙烯酯與乙酸乙烯酯以外之脂肪酸乙烯酯化合物組合使用較佳。
將含有乙烯酯系單體之單體組成物聚合時無特殊限制,可任意使用公知之聚合方法。例如可實施以甲醇、乙醇或異丙醇等碳數1~3之醇作為溶劑之溶液聚合。當然,也可進行塊狀聚合、乳化聚合、懸浮聚合。該溶液聚合時,乙烯酯系單體之進料方法,可使用分次進料、批次(batch)進料等任意方式。聚合反應使用偶氮雙異丁腈、過氧化乙醯、過氧化苯甲醯、過氧化月桂醯、偶氮雙二甲基戊腈、偶氮雙甲氧基戊腈等公知之自由基聚合觸媒進行。又,聚合反應溫度從40℃~約沸點之範圍選擇。
將該含有乙烯酯系單體之單體組成物聚合而獲得乙烯酯系聚合物之步驟,宜於含氧之條件下進行較佳。具體而言,邊導入含氧之氣體、或於聚合前事先導入含氧之氣體,將含有乙烯酯系單體之單體組成物聚合而獲得乙烯酯系聚合物較佳,邊導入含氧之氣體邊將含有乙烯酯系單體之單體組成物聚合而獲得乙烯酯系聚合物更佳。含氧氣體之導入方法不特別限定,例如宜利用吹入(鼓泡)導入為較佳。藉由邊導入含氧氣體、或於聚合前事先導入含氧氣體,並進行聚合,即使不經熱處理,也容易獲得雙鍵之含量比較高的PVA系樹脂。理由推測是因PVA系樹脂之聚合成長末端與氧反應,而形成醛基,之後發生脫乙酸反應所致之雙鍵導入的緣故。
亦即,藉由以該方法聚合,可獲得吸光度(B)會比較大且同時嵌段特徵值(A)之值比較小的PVA系樹脂。進而,即使不經熱處理,雙鍵之含量亦可較高,故獲得之PVA系樹脂、及該PVA系樹脂作為懸浮聚合用之分散劑使用時獲得之樹脂不易起黃變。因而依本發明之PVA系樹脂之製造方法,可獲得作為懸浮聚合用分散劑使用時聚合安定性、分散安定性優異、黃變抑制性優良的PVA系樹脂。
含氧氣體之導入方法可任意選擇,但宜以使氧濃度成為1質量%~9質量%之方式,導入經氮氣、氬氣、或氦氣這類鈍性氣體稀釋過的氣體較佳。氧濃度若少於1質量%則於反應系中未導入充分量的氧,容易變得難以獲得具有目標之甲醯基末端之PVA。又,若超過9質量%則會到達或超出乙酸乙烯酯之爆炸極限氧濃度(9~10質量%),易生安全上之顧慮。
含氧氣體對於反應系導入之方法可任意選擇,使用對於聚合液直接鼓泡而得之聚合液進行聚合、或邊對於聚合液直接鼓泡邊進行聚合之方法,能夠增大反應系內與氧之接觸面積故導入效率良好。
導入之氧之量可任意選擇,但每分鐘對單體量之氧供給量為25mL以下較佳。若超過25mL則於生產性方面不理想。又,若成為0.1mL以下則反應效率易變得不好,故氧供給量為0.1mL以上較佳。含氧氣體於聚合前預先導入時,取決於製造設備之尺寸、氣體流量而異,但含氧氣體之導入時間為0小時~3小時較理想,15分鐘~1小時更理想。
單體組成物聚合使用鏈移轉劑較佳。鏈移轉劑可列舉醇類例如:乙醇、甲醇、1-丙醇等,醛類例如:甲醛、乙醛、丙醛、丁醛、苯甲醛等,酮類例如:丙酮、甲乙酮、己酮、環己酮等。它們可單獨使用1種也可將2種以上組合使用。其中,考量聚合後之結構和最終產物類似之觀點,醇類及/或醛類較佳,尤其甲醇、乙醛較佳。
鏈移轉劑之添加量取決於添加之鏈移轉劑之鏈移轉常數、目的之PVA系樹脂之聚合度等而有若干差異,但能以任意之量添加。鏈移轉劑之添加量通常相對於乙烯酯系單體為0.1~200重量%較佳,更佳為0.5~150重量%,又更佳為1.0~130重量%,尤佳為1.3~100重量%。又,針對鏈移轉劑之進料方法,為初始之批次進料亦可,於聚合反應時進料亦可。鏈移轉劑藉由以任意的方法進料,能夠控制PVA系樹脂之分子量分布。
針對單體組成物,能將乙烯酯系單體單獨使用,但若有必要,也可將乙烯酯系單體、與可和乙烯酯系單體聚合之單體予以組合。亦即,本發明之PVA系樹脂可以為使用乙烯酯系單體及可和乙烯酯系單體聚合之單體共聚合成的乙烯酯系聚合物而獲得之改性PVA系樹脂。可和乙烯酯系單體聚合之單體,例如:(甲基)丙烯酸環氧丙酯、環氧丙基(甲基)烯丙醚、(甲基)丙烯酸3,4-環氧環己酯、烯丙基環氧丙醚等具有乙烯基與環氧基之單體;三烯丙氧基乙烯、丙二酸二烯丙基酯、氰尿酸三烯丙酯、異氰尿酸三烯丙酯、四烯丙氧基乙烷、酞酸二烯丙酯等有2個以上之烯丙基之單體;乙酸烯丙酯、乙醯乙酸乙烯酯、乙醯乙酸烯丙酯、二乙醯乙酸烯丙酯等烯丙酯系單體;乙醯乙醯氧基乙基(甲基)丙烯酸酯、乙醯乙醯氧基丙基(甲基)丙烯酸酯等乙醯乙醯氧基烷基(甲基)丙烯酸酯;乙醯乙醯氧基乙基巴豆酸酯、乙醯乙醯氧基丙基巴豆酸酯等乙醯乙醯氧基烷基巴豆酸酯;2-氰基乙醯乙醯氧基乙基(甲基)丙烯酸酯;二乙烯基苯;乙二醇二(甲基)丙烯酸酯、1,2-丙二醇二(甲基)丙烯酸酯、1,3-丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等伸烷基二醇(甲基)丙烯酸酯;三羥甲基丙烷三(甲基)丙烯酸酯;烯丙基(甲基)丙烯酸酯;(甲基)丙烯酸2-羥基乙酯、羥基丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯等羥基烷基(甲基)丙烯酸酯(烷基部分為C1~C10烷基,較佳為C1~C6烷基。);(甲基)丙烯腈等腈系單體;苯乙烯、α-甲基苯乙烯等苯乙烯系單體;乙烯、丙烯、1-丁烯、異丁烯等烯烴;氯乙烯、偏二氯乙烯、氟化乙烯、氟化亞乙烯等鹵化烯烴;乙烯磺酸等烯烴系單體;1,3-丁二烯、2-甲基丁二烯、1,3或2,3-二甲基-1,3-丁二烯、2-氯-1,3丁二烯等二烯系單體;3-丁烯-1-醇、4-戊烯-1-醇、5-己烯-1,2-二醇、甘油單烯丙醚等含羥基之α-烯烴類、及其醯基化物等衍生物;1,3-二乙醯氧基-2-亞甲基丙烷、1,3-二丙醯氧基-2-亞甲基丙烷、1,3-二丁醯氧基-2-亞甲基丙烷等羥基甲基亞乙烯二乙酸酯類;衣康酸、馬來酸、丙烯酸等不飽和酸類、其鹽或單或二烷酯;丙烯腈等腈類、甲基丙烯醯胺、二丙酮丙烯醯胺等醯胺類、乙烯磺酸、烯丙基磺酸、甲基烯丙基磺酸、AMPS(2-丙烯醯胺-2-甲基丙烷磺酸)等烯烴磺酸或其鹽等化合物、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三丙氧基矽烷、乙烯基三丁氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基甲基二乙氧基矽烷等乙烯基烷基二烷氧基矽烷;γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基三乙氧基矽烷等γ-(甲基)丙烯醯氧基丙基三烷氧基矽烷;γ-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷等γ-(甲基)丙烯醯氧基丙基烷基二烷氧基矽烷;乙烯基參(β-甲氧基乙氧基)矽烷、羥基甲基亞乙烯二乙酸酯。羥基甲基亞乙烯二乙酸酯之具體例可舉出1,3-二乙醯氧基-2-亞甲基丙烷、1,3-二丙醯氧基-2-亞甲基丙烷、1,3-二丁醯氧基-2-亞甲基丙烷等。又,可列舉3,4-二羥基-1-丁烯、3,4-二醯氧基-1-丁烯、3-醯氧基-4-羥基-1-丁烯、4-醯氧基-3-羥基-1-丁烯、3,4-二醯氧基-2-甲基-1-丁烯、4,5-二羥基-1-戊烯、4,5-二醯氧基-1-戊烯、4,5-二羥基-3-甲基-1-戊烯、4,5-二醯氧基-3-甲基-1-戊烯、5,6-二羥基-1-己烯、5,6-二醯氧基-1-己烯、甘油單烯丙醚、2,3-二乙醯氧基-1-烯丙氧基丙烷、2-乙醯氧基-1-烯丙氧基-3-羥基丙烷、3-乙醯氧基-1-烯丙氧基-2-羥基丙烷、甘油單乙烯醚、甘油單異丙烯醚、乙烯基碳酸伸乙酯、2,2-二甲基-4-乙烯基-1,3-二氧戊環等有二醇之化合物等。該等單體可以單獨使用或併用2種以上。
又,「(甲基)丙烯酸酯」係指「丙烯酸酯及/或甲基丙烯酸酯」,針對「(甲基)烯丙基」、「(甲基)丙烯酸基」亦同。
可和乙烯酯系單體聚合之單體之含量,在單體組成物中為20莫耳%以下較佳,10莫耳%以下更佳。
皂化可依公知之方法進行,通常係使乙烯酯系聚合物溶於醇及酯,並於鹼觸媒或酸觸媒之存在下進行。醇,例如:甲醇、乙醇、丁醇等碳數1~6之醇。酯,例如:乙酸甲酯、乙酸乙酯、乙酸丁酯等碳數3~8之酯。皂化時使用之醇及酯能以任意之組合使用,考量生產性之觀點,使用甲醇及乙酸甲酯較佳。
針對醇及酯中之乙烯酯系聚合物之濃度,考量溶解率之觀點,從1~70重量%之範圍中選擇較佳。
鹼觸媒可使用例如:氫氧化鈉、氫氧化鉀、甲醇化鈉、乙醇化鈉、甲醇化鉀等鹼金屬之氫氧化物、醇鹽之鹼觸媒。酸觸媒可使用例如:鹽酸、硫酸等無機酸水溶液、對甲苯磺酸等有機酸。該觸媒之使用量相對於乙烯酯系單體設為1~100毫莫耳當量較佳,更佳為1~40毫莫耳當量,又更佳為1~30毫莫耳當量。觸媒之使用量若過少,皂化進展到成為目標皂化度會有變得困難的傾向,又,觸媒之使用量過多,皂化反應性也不易有進一步提升,故不理想。
實施皂化時之反應溫度無特殊限制,例如:10~70℃較理想,更佳為從20~50℃之範圍選擇。
本發明之PVA系樹脂也可是藉由使獲得之PVA系樹脂進行後改性而獲得之改性PVA系樹脂。利用後改性製造改性PVA系樹脂之方法,例如:將PVA系樹脂進行乙醯乙酸酯化、縮醛化、胺甲酸酯化、醚化、接枝化、磷酸酯化、氧基伸烷基化之方法等。
如上述,皂化獲得之PVA系樹脂之後乾燥,利用該皂化獲得之PVA系樹脂也可含有2~3價之金屬之鹽及氫氧化物中之至少一者。
2~3價之金屬,例如:鎂、鈣、鋅、鋁等。此等金屬之鹽或氫氧化物之具體例,例如:乙酸鎂4水合物、乙酸鈣、丙酸鈣、丁酸鎂、碳酸鎂、氫氧化鎂、乙酸鋅、氫氧化鋁等,可單獨使用1種也可將2種以上組合使用。其中,考量溶於水及/或甲醇等而於工業上容易操作之觀點,乙酸鎂4水合物、乙酸鈣較佳。
含有2~3價之金屬之鹽及/或氫氧化物之方法不限定,例如:可將上述化合物直接添加在皂化前之糊劑、皂化後之漿液等。較佳為使其溶於甲醇、乙醇、丙醇等醇、或水而成為約3~15重量%之濃度之溶液狀,添加到皂化後之PVA系樹脂之漿液並使其分配於PVA系樹脂之方法。
如上述獲得之PVA系樹脂,於皂化後乾燥,成為粉末狀之PVA系樹脂。乾燥方法,例如:減壓乾燥、常壓乾燥、熱風乾燥等。該乾燥時間通常為10分鐘~20小時,較佳為1小時~15小時,乾燥溫度通常為40~140℃,更佳為40~120℃,尤佳為50℃以上且未達100℃。
[用途]
如上述獲得之本發明之PVA系樹脂,因著色(黃變)受抑制,故色相優異,適用在各式各樣的用途。本發明之PVA系樹脂之用途,例如以下。
(1)成形物相關:纖維、薄膜、板片、管路、筒管、防漏膜、暫時性皮膜、化學飾帶(chemical lace)用、水溶性纖維等。
(2)黏接劑相關:木材、紙、鋁箔、塑膠等黏接劑、黏著劑、再濕劑、不織布用黏結劑、石膏板、纖維板等各種建材用黏結劑、各種粉體造粒用黏結劑、水泥、灰泥用添加劑、熱熔型黏接劑、感壓黏接劑、陰離子性塗料之固接劑等。
(3)被覆劑相關:紙之透明塗劑、紙之顏料塗劑、紙之內添上漿劑、纖維製品用上漿劑、經紗糊劑、纖維加工劑、皮革加工劑、塗料、防霧劑、金屬抗腐蝕劑、鋅鍍敷用光澤劑、抗靜電劑、導電劑、暫時性塗料等。
(4)疏水性樹脂用摻混劑相關:疏水性樹脂之抗靜電劑、及親水性賦予劑、複合纖維、薄膜其他成形物用添加劑等。
(5)分散劑相關:感熱發色層用塗佈液之顯色劑用分散劑、塗料、墨汁、水彩、黏接劑等顏料分散安定劑、氯乙烯、偏二氯乙烯、苯乙烯、(甲基)丙烯酸酯、乙酸乙烯酯等各種乙烯基化合物之懸浮聚合用分散安定劑等。
(6)乳化分散安定劑相關:各種丙烯酸系單體、乙烯性不飽和化合物、丁二烯性化合物之乳化聚合用乳化劑、聚烯烴、聚酯樹脂等疏水性樹脂、環氧樹脂、石蠟、瀝青(bitumen)等後乳化劑等。
(7)增黏劑相關:各種水溶液、乳劑、石油挖掘流體之增黏劑等。
(8)凝聚劑相關:水中懸浮物及溶存物之凝聚劑、木漿、漿液之濾水劑等。
(9)交換樹脂等相關:離子交換樹脂、螯合物交換樹脂、離子交換膜等。
(10)其他:土壤改良劑、感光劑、感光性光阻樹脂等。
上述當中,尤其本發明之PVA系樹脂於乙酸乙烯酯、氯乙烯等各種乙烯基化合物之懸浮聚合用分散安定劑有用,尤其作為氯乙烯系化合物之懸浮聚合用分散安定劑有用。
[分散劑]
本發明之PVA系樹脂作為分散劑使用時,被分散體可列舉例如:聚合性單體、粉體等。本發明之PVA系樹脂尤其作為聚合性單體係被分散體之懸浮聚合用之分散劑較佳。成為懸浮聚合之對象之聚合性單體,例如:氯乙烯、鹵化亞乙烯、乙烯醚、乙酸乙烯酯、苯甲酸乙烯酯、丙烯酸、甲基丙烯酸、馬來酸或其酐、乙烯、丙烯、苯乙烯等。其中,本發明之PVA系樹脂適合使用在氯乙烯之均聚合、或氯乙烯與可和氯乙烯共聚合之單體之共聚合。
[懸浮聚合用分散劑]
以下針對本發明之PVA系樹脂作為懸浮聚合用分散劑的情形詳述。本發明之PVA系樹脂之使用量可因應懸浮聚合之單體適當調整,例如使用在氯乙烯系單體之懸浮聚合時,例如相對於氯乙烯系單體100重量份使用5重量份以下較佳,0.01~1重量份更佳,又更佳為0.02~0.2重量份。其使用量若過多,會有不作為分散劑作用之PVA系樹脂增加之傾向。
懸浮聚合時,例如:於水或加熱水介質添加本發明之PVA系樹脂作為分散劑,使氯乙烯系單體分散並於油溶性觸媒存在下聚合較佳。
PVA系樹脂之添加方法可列舉:以粉末形式直接添加、將PVA系樹脂以溶於水、或醇、酮、酯等有機溶劑、或該等有機溶劑與水之混合溶劑成溶液之狀態添加之方法、或以PVA系樹脂分散於上述溶劑成分散液之狀態添加之方法。針對添加之時間點,可於聚合初始批次添加,也可於聚合途中分次添加。
針對其他添加劑,也可併用公知之安定劑,例如高分子物質。高分子物質可列舉本發明之PVA系樹脂以外之PVA系樹脂。針對該PVA系樹脂,可使用未改性之PVA、上述改性PVA系樹脂等。
針對聚合助劑可列舉各種界面活性劑或無機分散劑等,也可將本發明之PVA系樹脂作為聚合助劑使用。
聚合觸媒只要是油溶性之觸媒皆可,可以使用例如:過氧化苯甲醯、過氧化月桂醯、過氧化二碳酸二異丙酯、α,α’-偶氮雙異丁腈、α,α’-偶氮雙-2,4-二甲基-戊腈、乙醯基環己基磺醯基過氧化物或該等之混合物。
[實施例]
以下利用實施例對本發明更詳細說明,但本發明在不超過其要旨之限度內不限於下列實施例。又,「份」、「%」等係重量基準。
(實施例1)
[本發明之PVA系樹脂(PVA-1)之製造]
將乙酸乙烯酯100重量份、甲醇100重量份進料到聚合槽,邊以120mL/分對於液相供給氧氣/氮氣(5:95、體積比)混合氣體邊加熱,於沸點下,於聚合槽進料相對於乙酸乙烯酯為0.4重量%之偶氮雙異丁腈(AIBN),開始聚合。反應時間約7小時後,在聚合率到達73.2重量%之時點停止聚合。之後,去除未聚合之乙酸乙烯酯,依常法皂化,獲得PVA系樹脂(聚合度590、皂化度71.8莫耳%)。
<嵌段特徵值之測定>
依上述方法測定PVA系樹脂(PVA-1)之嵌段特徵值(A1
)之值。結果示於表1。
<紫外線吸收光譜之測定>
製作PVA系樹脂(PVA-1)之0.1%水溶液。使用紫外可見近紅外分光光度計(日本分光(股)公司製「V-560」(商品名)),測定PVA系樹脂之0.1%水溶液於320nm之吸光度(B1
)。又,係使用厚度1cm之試樣容器(光析管)。結果示於表1。進一步,算出PVA系樹脂(PVA-1)製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B1
)相對於嵌段特徵值(A1
)之比(B1
/A1
)。結果示於表1。
<黃色指數(YI值)之測定>
製作PVA系樹脂(PVA-1)之0.1%水溶液。使用KONICAMINOLTA(股)公司製測色計「CM-3600A」(商品名)測定該水溶液之YI值。結果示於表1。
(實施例2)
[本發明之PVA系樹脂(PVA-2)之製造]
將乙酸乙烯酯100重量份、乙醛2.0重量份、甲醇4.9重量份進料到聚合槽,邊以120mL/分對於液相供給氧氣/氮氣(5:95、體積比)混合氣體邊加熱,於沸點下,於聚合槽進料相對於乙酸乙烯酯為0.01重量%之偶氮雙異丁腈(AIBN),開始聚合。反應時間約11.5小時後,在聚合率到達61.9重量%之時點停止聚合。之後,去除未聚合之乙酸乙烯酯,依常法皂化,獲得PVA系樹脂(聚合度760、皂化度75.8莫耳%)。針對獲得之PVA系樹脂(PVA-2),和實施例1同樣測定嵌段特徵值(A2
)、320nm之紫外線吸收光譜(B2
)、YI值。結果示於表1。
(比較例1)
[PVA系樹脂(PVA-3)之製造]
將乙酸乙烯酯100份、乙醛1.6份、甲醇4.7份及相對於乙酸乙烯酯為0.0092%之過氧化乙醯(APO)進料到聚合槽,進行氮氣取代。之後加熱,於沸點下使聚合開始,於反應時間約7小時後,到達聚合率80.0%之時點停止聚合。然後去除未聚合之乙酸乙烯酯,將獲得之聚合物以氫氧化鈉依常法皂化。於樹脂成分12%之PVA系樹脂(聚合度630、皂化度71.7莫耳%)之皂化漿液中加入使得抖落(shake off)後之乙酸鈉量相對於PVA系樹脂成為1重量%之量之乙酸鈉,並進行抖落。然後,於上述製備之PVA系樹脂添加作為金屬化合物之乙酸鎂4水合物之20%甲醇溶液,使乙酸鎂相對於PVA系樹脂成為2重量%,之後乾燥,獲得含有乙酸鎂2重量%、乙酸鈉1重量%之PVA系樹脂。再對於獲得之樹脂於140℃實施熱處理,獲得PVA系樹脂(PVA-3)。針對獲得之PVA系樹脂(PVA-3),和實施例1同樣測定嵌段特徵值(A3
)、於320nm之紫外線吸收光譜(B3
)、YI值。結果示於表1。
(比較例2)
[PVA系樹脂(PVA-4)之製造]
熱處理於110℃進行,除此以外和比較例1同樣進行,獲得PVA系樹脂(PVA-4)。針對獲得之PVA系樹脂(PVA-4),和實施例1同樣測定嵌段特徵值(A4
)、於320nm之紫外線吸收光譜(B4
)、YI值。結果示於表1。
(比較例3)
[PVA系樹脂(PVA-5)之製造]
將乙酸乙烯酯100份、乙醛1.6份、甲醇4.7份及相對於乙酸乙烯酯為0.0092%之過氧化乙醯(APO)進料到聚合槽,進行氮氣取代。之後加熱,於沸點下使聚合開始,於反應時間約7小時後,到達聚合率80.0%之時點停止聚合。然後去除未聚合之乙酸乙烯酯,將獲得之聚合物以氫氧化鈉依常法皂化。於樹脂成分12%之PVA系樹脂(聚合度630、皂化度71.7莫耳%)之皂化漿液中加入使得抖落後之乙酸鈉量相對於PVA系樹脂成為1重量%之量之乙酸鈉,並進行抖落。然後,於上述製備之PVA系樹脂添加作為金屬化合物之乙酸鎂4水合物之20%甲醇溶液,使乙酸鎂相對於PVA系樹脂成為2重量%,之後乾燥,獲得含有乙酸鎂2重量%、乙酸鈉1重量%之PVA系樹脂(PVA-5)。針對獲得之PVA系樹脂(PVA-5),和實施例1同樣測定嵌段特徵值(A5
)、於320nm之紫外線吸收光譜(B5
)、YI值。結果示於表1。
[表1]
PVA系樹脂 | 皂化度 (mol%) | 嵌段特徵值(A) | 320nm之紫外線吸收光譜(B) | (B/A) | YI值 | |
實施例1 | PVA-1 | 71.8 | 0.37 | 0.31 | 0.84 | 1.81 |
實施例2 | PVA-2 | 71.8 | 0.37 | 0.45 | 1.21 | 1.89 |
比較例1 | PVA-3 | 72.4 | 0.53 | 0.40 | 0.75 | 4.24 |
比較例2 | PVA-4 | 72.4 | 0.41 | 0.11 | 0.27 | 1.54 |
比較例3 | PVA-5 | 72.4 | 0.39 | 0.08 | 0.21 | 1.52 |
依表1之結果,實施例1、2之PVA系樹脂相較於比較例1~3之PVA系樹脂,能兼顧雙鍵量高及嵌段特徵值之值小。此外,實施例1、2之PVA系樹脂,相較於雙鍵量較接近之比較例1之PVA系樹脂,YI值更低。如此,實施例1、2可以獲得聚合時之聚合安定性、分散性及黃變抑制性優異之PVA系樹脂。
已就本發明詳細且參照特定實施形態說明,但該技術領域中具通常知識者知曉可不脫離本發明之精神及範圍而加諸各式各樣的變更、修正。本申請案係基於2020年1月16日提申之日本專利申請案(日本特願2020-005372),其內容納入於此作為參照。
[產業利用性]
本發明之PVA系樹脂因雙鍵量多,當作為懸浮聚合用分散劑使用時懸浮聚合安定性優異,進而作為各種分散劑使用時,聚合時之聚合安定性優異。又,嵌段特徵值之值小,因此本發明之PVA系樹脂作為各種分散劑使用時,界面活性能力高而分散性優異。本發明之PVA系樹脂尤其作為氯乙烯系單體之懸浮聚合用分散劑有用。
Claims (5)
- 一種聚乙烯醇系樹脂,其嵌段特徵值(A)小於0.4,且該聚乙烯醇系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)為0.2以上。
- 如請求項1之聚乙烯醇系樹脂,其中,該聚乙烯醇系樹脂製成0.1重量%水溶液時測得之紫外線吸收光譜中之320nm之吸光度(B)相對於該嵌段特徵值(A)之比(B/A)為0.6以上。
- 一種分散劑,係由如請求項1或2之聚乙烯醇系樹脂構成。
- 一種懸浮聚合用分散劑,係由如請求項1或2之聚乙烯醇系樹脂構成。
- 一種如請求項1或2之聚乙烯醇系樹脂之製造方法,包括邊導入含氧氣體邊將含乙烯酯系單體之單體組成物進行聚合而獲得乙烯酯系聚合物之步驟。
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