TW524808B - Water-borne resin compositions of polymethacrylates possessing hydrophilic pendant groups - Google Patents

Water-borne resin compositions of polymethacrylates possessing hydrophilic pendant groups Download PDF

Info

Publication number
TW524808B
TW524808B TW85109006A TW85109006A TW524808B TW 524808 B TW524808 B TW 524808B TW 85109006 A TW85109006 A TW 85109006A TW 85109006 A TW85109006 A TW 85109006A TW 524808 B TW524808 B TW 524808B
Authority
TW
Taiwan
Prior art keywords
water
based resin
homopolymer
patent application
solid content
Prior art date
Application number
TW85109006A
Other languages
Chinese (zh)
Inventor
Hou-Shian Ju
Dau-Jung Fu
Original Assignee
Hou-Shian Ju
Dau-Jung Fu
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hou-Shian Ju, Dau-Jung Fu filed Critical Hou-Shian Ju
Priority to TW85109006A priority Critical patent/TW524808B/en
Application granted granted Critical
Publication of TW524808B publication Critical patent/TW524808B/en

Links

Landscapes

  • Paper (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Using a mixture of polyvinyl alcohol (or alcohols with carbon numbers of at least six) and anionic surfactant (e.g., sodium dodecyl sulfate) as the emulsifier, water-borne polymer resins with a solid as high as 10% wt of poly(2-hydroxyethyl methacrylate) and poly(hydroxypropyl methacrylate) were prepared in the emulsion polymerization of respective monomers without forming hydrogel by controlling the nucleation rate via choosing an initiator with a low initiation rate.

Description

524808 五、發明説明（ 本創作係以乳化聚合程序製備具i〇%wt固含量的聚 (甲基丙烯酸-2 -氫氧基乙酯）（poly(2 —hydr〇xyethyl 請先閱讀背面之注意事項再填寫本頁 methacry late)，PHEMA)與聚（甲基丙烯酸氫氧基丙酯） (P〇ly(hyd]：〇Xypropyl methacryiate)，PHPMA)水性樹脂。 分散粒子的粒徑在0.1 5-0. 30#。 乳化聚合反應所使用的單體通常為低水溶性者，諸如 笨乙烯、丁二烯等。隨著單體水溶性的增加，乳化聚合的的 困難度亦增加，所得安定乳液·的固含量極限則相對較低。因 此，多數高水溶性單體多半不以乳化聚合方式製備；即使以 礼化聚合法製備，其能製備的固含量亦不高◦例如：丙烯晴 (acrylonitrile，AN)，於 5(rC 時的水溶解度= 8·5%，其 所製備樹脂的固含量大約只達1 1 %〔 1〕。 具親水性懸掛基團的甲基丙烯酸酯有超大的水溶 性。例如：甲基丙烯酸_ 2 _氫氧基乙酯（ΗΕΜΑ)可以和水以 任何比例混合，其在水中之溶解度視同無窮大〔2〕。較精 確之數據則為ΗΕΜΑ以81%wt之濃度溶解在水中〔3〕。總之， 此類型的單體的溶解度遠超過一般所提到的高水溶性單體 (例如：AN )。 經濟部中央標準局員工消費合作社印製 在服11八之水相聚合會輕易地形成水凝膠（^打〇狀1)。 經乳化聚合反應製備PHEMA水性樹脂，在超出一定的固含量 則易开^成水凝知，而不是分散的水性樹脂。起因於它的超大 水洛性，且其乳化聚合大部分為共聚合◦因此，HEMA以乳化 ^合方式製備具相當固含量的水性樹脂上的技術的突破有 其重要性’甚且代表乳化聚合技術的一個新指標。 本紙張尺度標準（cns Α7524808 V. Description of the invention (This creation is based on the emulsification polymerization procedure to prepare poly (methacrylic acid-2-hydroxyloxyethyl) with a solid content of i0% wt. (Poly (2-hydroxyxyethyl) Please read the note on the back first Fill in the matter again on this page (methacry late), PHEMA) and poly (hydroxypropyl methacrylate) (Poly (hyd): 0Xypropyl methacryiate), PHPMA). The particle size of the dispersed particles is 0.1 5- 0. 30 #. The monomers used in the emulsion polymerization are usually those with low water solubility, such as stupid ethylene, butadiene, etc. As the water solubility of the monomers increases, the difficulty of emulsion polymerization also increases, and the resulting stable emulsion · The solid content limit is relatively low. Therefore, most of the highly water-soluble monomers are mostly not prepared by emulsion polymerization; even if they are prepared by etiquette polymerization, the solid content that can be prepared is not high. For example: acrylonitrile , AN), water solubility at 5 (rC = 8.5%, the solid content of the resin prepared is only about 11% [1]. Methacrylates with hydrophilic pendant groups have very large water solubility Properties, such as: methacrylic acid _ 2 _ Hydroxyethyl (ΗΕΜΑ) can be mixed with water in any ratio, and its solubility in water is considered to be infinite [2]. A more accurate data is that ΗΕΜΑ is dissolved in water at a concentration of 81% by weight [3]. In short, this type of monomer The solubility is much higher than the commonly mentioned highly water-soluble monomers (for example: AN). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the water-phase polymerization will easily form a hydrogel (^ 打 〇 状) 1). PHEMA water-based resin is prepared by emulsification polymerization reaction. When it exceeds a certain solid content, it is easy to form water coagulation, rather than dispersed water-based resin. It is due to its super hydroscopicity, and most of its emulsion polymerization is Copolymerization ◦ Therefore, the breakthrough of HEMA's technology in the preparation of water-based resins with a relatively solid content by means of emulsification and blending is of great importance, and even represents a new indicator of emulsification polymerization technology. This paper standard (cns Α7)

五、發明説明（2 ) 524808 PHEMA微球粒製備方法有：乳化聚合〔4 —6〕、懸浮聚合〔7 —n〕 與分散聚合〔12〕等。絕對多數的反應為HEMA的共聚合反應。 懸浮聚合多半使用EGDMA為交連劑；以聚乙烯醇（pvA)，MgO 或MgOH等為懸浮安定劑；且反應介質除水相外，有些則含有 機相（包含甲笨與正己烷〔8〕，異丁醇〔9〕，環己烷〔11〕 等）。乳化聚合包括核（PHEMA )-殼（聚苯乙烯）產品〔4， 5〕和以HEMA充含官能基單體進行苯乙烯的無乳化劑的乳化 聚合〔6〕。在HEMA的分散聚合中則曾使用一系列的有機溶 劑〔12〕。 在以水為介質的HEMA懸浮聚合中雖可選擇使用pvA當 作懸浮安定劑，但產生的分散液粒子粒徑甚大（〇 . 8_ 1 〇 ")， 不安定，隔夜即形成水凝膠。 综合上述，吾人尚未發現有關在不需使用有機介質的 情況’經乳化聚合能夠製備粒徑在〇 · 5 "以下、固含量在4〇/〇 以上的PHEMA及PHPMA的各別水性樹脂的報導。 本創作之主要目的乃經調整乳化聚合配方中使用的 起始劑、乳化劑之種類與組成，以製的各別 水性樹脂；且此等水性樹脂中分散粒子的粒徑可小到m u ° 在HEMA或HPMA的乳化聚合程序中，吾人使用PVA與十 二 基硫酸鈉（sodium dodecyl sulfate, SDS)的混合乳 化劑’限制SDS於一定濃度範圍，且選擇在水中起始速率 低的起始劑（例如：2,2‘-azobis (isobutyronitrile)， AIBN) 〇 2 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention (2) 524808 PHEMA microspheres are prepared by emulsification polymerization [4-6], suspension polymerization [7-n], and dispersion polymerization [12]. The absolute majority of the reactions are copolymerization of HEMA. Most suspension polymerization uses EGDMA as a cross-linking agent; polyvinyl alcohol (pvA), MgO or MgOH as suspension stabilizers; and the reaction medium contains an organic phase (including methylbenzyl and n-hexane [8], in addition to the aqueous phase, Isobutanol [9], cyclohexane [11], etc.). Emulsion polymerization includes core (PHEMA) -shell (polystyrene) products [4, 5] and emulsifier-free emulsification polymerization of styrene with HEMA-containing functional monomers [6]. A series of organic solvents have been used in HEMA's dispersion polymerization [12]. In the HEMA suspension polymerization using water as the medium, although pvA can be selected as a suspension stabilizer, the particle size of the resulting dispersion particles is very large (0.8_10), and it is unstable, and a hydrogel is formed overnight. Based on the above, we have not found any reports about the use of organic media without the need to use PHEMA and PHPMA to produce individual aqueous resins with particle sizes below 0.5 " and solid content above 40 / 〇 after emulsification polymerization. . The main purpose of this creation is to adjust the types and composition of the initiators and emulsifiers used in the emulsion polymerization formula to make individual water-based resins; and the particle size of the dispersed particles in these water-based resins can be as small as mu ° in In the emulsification polymerization process of HEMA or HPMA, we use a mixed emulsifier of PVA and sodium dodecyl sulfate (SDS) to limit the SDS to a certain concentration range, and choose an initiator with a low onset rate in water ( For example: 2,2'-azobis (isobutyronitrile), AIBN) 〇2 This paper size applies to China National Standard (CNS) Α4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

經濟部中央標準局員工消費合作社印製 524808 A7 B7 五、發明説明（3 ) Η Ε Μ A與Η Ρ Μ A具有極向水溶性。此等單體入水後，可以 和水5t全互溶。起始劑分解後，在水相中與單體開始聚合。 开y成的聚合物卻為低水溶性物質Q藉配方中的混合乳化劑安 定聚合物，可形成粒徑較小的安定水性樹脂。 茲舉批式實驗例子如下，以説明相關之技術。 基本配方例 成份 克 HEMA(或 HPMA) 20 SDS 0.3 PVA 0·5， 1.0，或 1·5 AIBN 0.2 水 180 (請先閱讀背面之注意事項再填寫本頁) 、1' 經濟部中夬榡隼局員工消費合作社印製 以25 Oml四口燒瓶配備機械攪拌裝置作為反應器。程序 採恆溫50°C，以水浴加熱。將SDS與PVA加入已事先置入1⑽克 水的反應器中，以240rpm速率攪拌，升溫到50°C ，並保持恒 溫直到反應結束。3 0分鐘後，再加入AIBN，並繼續攪拌3 〇分 鐘◦最後加入單體，開始反應。保持恆溫、恆速攪拌直到反 應結束。反應時間約9 0 -1 2 0分鐘。可得安定的水性樹脂。以 雷射粒子粒徑測定儀測得樹脂中的分散液粒子粒徑約〇 . 10.25// 〇 3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 524808 A7 B7 V. Description of the Invention (3) Ε Μ A and Η Ρ A are extremely water-soluble. After these monomers enter water, they can be completely miscible with 5t of water. After the initiator is decomposed, polymerization with the monomers begins in the aqueous phase. The polymer formed by Y is a low-water-soluble substance. By using a mixed emulsifier stabilizer polymer in the formulation, a stable water-based resin with a smaller particle size can be formed. Here are some examples of batch experiments to illustrate the related techniques. Basic formulation example ingredients HEMA (or HPMA) 20 SDS 0.3 PVA 0.5, 1.0, or 1.5 AIBN 0.2 water 180 (Please read the precautions on the back before filling this page), 1 'Ministry of Economic Affairs 夬 榡 隼Bureau employee consumer cooperative printed 25 Oml four-neck flask equipped with a mechanical stirring device as a reactor. Procedure Use a constant temperature of 50 ° C and heat in a water bath. SDS and PVA were added to a reactor that had been previously placed in 1 g of water, stirred at 240 rpm, warmed to 50 ° C, and kept at a constant temperature until the reaction was completed. After 30 minutes, add AIBN again and continue stirring for 30 minutes. Finally, add the monomer to start the reaction. Maintain constant temperature and constant speed until the reaction is complete. The reaction time is about 90 to 120 minutes. A stable water-based resin is obtained. The particle size of the dispersion particles in the resin measured with a laser particle size analyzer is about 0.125 // 〇 3 This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm)

524808 合 A7 B7 五、發明説明（4 反應溫度在35-9(rc的範圍，皆可順利完成乳化聚 ^ 在所有配方中，PVA的分子量有多種選擇，例如··一 萬、-禺五千、二萬二千、七萬二千或十萬者。選擇任何一 種與SDS搭配，皆可順利完成乳化聚合。 在配方中，若以脂肪醇（例如：十醇、十二醇、十六醇、 十八醇等）取A PVA，進行乳化聚合反應，亦可順利完成^化 聚合。即使以乙醇或丁醇亦爾PVA，於乳化聚合中順利 製備水性樹脂；唯選擇的固含量要低一些。 改良批式乳化聚合反應，採分批加入單體的方式，亦 可提高水性樹脂固含量；但樹脂的安定性會逐漸惡化，粒徑 迅速變大。 另一種製備具相當固含量的!^£1^與PHPMA樹脂的方法 乃是先以乳化聚合反應製備低固含量樹脂，再以眞空蒸餾方 式移走部分水量，提高樹脂最終固含量。此雖是一個變通的 方式，彳一在眞工蒸餘時仍可能因安定性會逐漸惡化，粒徑迅 速變大。因此，關鍵仍在樹脂配方中乳化劑的抉擇。 本創作哭破極高水溶性單體在乳化聚合反應中所能製 備的水性樹脂固含量範圍限制，成功地製備固含量可達1〇%wt 的PHEMA與PHPMA兩種水性樹脂。本創作重要的特點有··（ 1) 使用PVA與SDS混合乳化劑明顯地改善單獨使用pvA當乳化劑 於乳化聚合反應時面臨的缺陷（即粒子粒徑大，及反應後迅速 形成水凝膠的問題）◦( 2)使用油溶性起始劑成功地壓制水相 4 本紙張尺度適用中國國豕標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)524808 A7 B7 V. Description of the invention (4 The reaction temperature is in the range of 35-9 (rc), and the emulsification polymerization can be successfully completed. , 22,000, 72,000, or 100,000. Either one can be used with SDS to successfully complete the emulsion polymerization. In the formula, if fatty alcohols (such as: ten alcohol, dodecanol, cetyl alcohol) , Stearyl alcohol, etc.) Taking A PVA and carrying out the emulsion polymerization reaction, the polymerization can also be successfully completed. Even with ethanol or butanol YEL PVA, the water-based resin can be successfully prepared in the emulsion polymerization; only the solid content selected is lower . Improved batch emulsion polymerization reaction, adding monomers in batches can also increase the solid content of water-based resins; but the stability of the resin will gradually deteriorate, and the particle size will rapidly increase. Another preparation has a fairly solid content! ^ The method of £ 1 ^ and PHPMA resin is to first prepare a low solid content resin by emulsification polymerization, and then remove part of the water by air distillation to increase the final solid content of the resin. Although this is a workaround, the Steam It is still possible that the stability will gradually deteriorate and the particle size will rapidly increase. Therefore, the key is still the choice of emulsifier in the resin formulation. This creation cries out the water-soluble resin that can be prepared in the emulsion polymerization reaction of extremely highly water-soluble monomers. The solid content range was limited, and PHEMA and PHPMA two kinds of water-based resins with a solid content of 10% wt were successfully prepared. The important characteristics of this creation are (1) the use of PVA and SDS mixed emulsifiers significantly improves the use of pvA alone. Defects of emulsifiers during emulsification polymerization (that is, the large particle size and the problem of rapid formation of hydrogels after the reaction) ◦ (2) the use of oil-soluble initiators to successfully suppress the water phase 4 This paper is applicable to China豕 Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

經濟部中央標準局員工消費合作社印製 524808 A7 _________B7 五、發明説明（5 ) (請先閱讀背面之注意事項再填寫本頁) 中起始的自由基數量與其後成核數量，因此避免水凝膠之形 成。（3)樹脂製備過程中，不必使用有機溶劑當介質，符合 環境保護減少揮發性溶劑使用之要求與生物醫學工程上降低 不必要有毒物質的需求。 1. I.Piirma, J.C.Chang and M.Daneshvar, Polymer Preprint, ACS,Div. Polym. Chem., 21(1),219(1990). 2· O.Wichterle/’Hydrogel，，，ρ·273-291, Vol· 1 in Encyclopedia of Polymer Science and Technology, ed. by H.F. Mark, N.G.Gaylord and N.M.Bikales, Wiley-Interscience，New York, 1970. 3. T.H.Chieng, L.M.Gan, C.H. Chew and S.C.Ng, Polymer, 3i(10), 1941-46(1995). 4 . S.Kamei，M.Okubo, T.Matsumoto, J.Appl.Polym.Sci., 34^ 1439-1446(1987). 5 · S·Kamei，M·Okubo，T·Matsumoto，J · Po1ym·Sci·，A 24， 經濟部中央標隼局員工消費合作社印製 3109-3116(1986). 6· S.A.Chen and H.S、Chang, J.Polym.Sci. AM_，2547-2561 (1990). 7. D.Horak, F. Lednicky, V.Rehak and F.Svec, J. Appl. Polym.Sci., 49,2041-2050(1993). 5 本紙張尺度適用中國國家標準（CNS)A4規格（21〇X 297公釐） 5^4808 Α7 Β7 五、 經濟部中央標準局員工消費合作社印製 發明説明（6 ) 8 ·劉豐志，蔡瑞瑩，王盈錦，中華民國高分子研討會論文 集，殳，365-367( 1 993 )· M.Y.Arica, V.Hasirci and N.G. A1aeddinog 1u, Biomaterials,1 6( 1 0 ), 761-768 ( 1 995). 1〇· M.K i rem i tc i and H.Cukurova, Polymer International, 30,357-361(1993)· 11 · 0 · Okay and C · Gurun，J.Appl.Polym.Sci., 46^, 401-410 (1992). 12. S.Hosaka, Y.Murao, H.Tamaki, S.Masuko, K.Miuraand Y . Kawabata , Polymer International，3_0 , 505-51 1 (1993). 、\st» (讀先閱讀背面之注意事項再填寫本頁Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 524808 A7 _________B7 V. Description of the invention (5) (Please read the precautions on the back before filling this page) The initial free radical quantity and subsequent nucleation quantity, so avoid condensation Formation of glue. (3) In the resin preparation process, it is not necessary to use organic solvents as the medium, which meets the requirements of environmental protection to reduce the use of volatile solvents and reduces the need for unnecessary toxic substances in biomedical engineering. 1. I. Piirma, JCChang and M. Daneshvar, Polymer Preprint, ACS, Div. Polym. Chem., 21 (1), 219 (1990). 2. O. Wichterle / 'Hydrogel ,,, ρ · 273- 291, Vol · 1 in Encyclopedia of Polymer Science and Technology, ed. By HF Mark, NGGaylord and NMBikales, Wiley-Interscience, New York, 1970. 3. THChieng, LMGan, CH Chew and SCNg, Polymer, 3i (10), 1941-46 (1995). 4. S.Kamei, M.Okubo, T.Matsumoto, J.Appl.Polym.Sci., 34 ^ 1439-1446 (1987). 5 · S · Kamei, M. Okubo, T. Matsumoto, J. Po1ym, Sci, A 24, Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, 3109-3116 (1986). 6. SAChen and HS, Chang, J. Polym.Sci AM_, 2547-2561 (1990). 7. D. Horak, F. Lednicky, V. Rehak and F. Svec, J. Appl. Polym. Sci., 49, 2041-2050 (1993). 5 paper sizes Applicable to China National Standard (CNS) A4 specification (21 × 297 mm) 5 ^ 4808 Α7 Β7 5. The invention description printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (6) 8 · Liu Fengzhi, Cai Ruiying, Wang Yingjin, the Republic of China High Proceedings of the Molecular Symposium, 殳, 365 -367 (1 993) MYArica, V. Hasirci and NG A1aeddinog 1u, Biomaterials, 16 (1 0), 761-768 (1 995). 1 · MK i rem i tc i and H. Cukurova, Polymer International, 30, 357-361 (1993) .11.0 Okay and C. Gurun, J. Appl. Polym. Sci., 46 ^, 401-410 (1992). 12. S. Hosaka, Y. Murao, H. Tamaki, S. Masuko, K. Miuraand Y. Kawabata, Polymer International, 3_0, 505-51 1 (1993)., \ St »(Read the precautions on the back before filling out this page

6 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐)6 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm)

Claims (1)

524808 ί公告本丨 Α8 Β8 C8 D8 a 六- 經濟部中央標準局員工消費合作社印製 、申請專利範圍 一 1. 一種製備聚甲基丙烯酸酯均聚物水性樹脂之乳化聚合方法，其特 徵爲：1)使用水爲載體;2)使用之單體爲甲基丙烯酸-2-氫氧基 乙酯(HEMA)，或甲基丙烯酸氫氧基丙酯(HPMA); 3)使用之乳化 劑包含A及B，其中A爲聚乙烯醇(PVA)或C6以上之脂肪醇，B爲燒 基硫酸鹽、院基磺酸鹽、或烷基苯磺酸鹽陰離子型界面活性劑;4) 使用之起始劑爲低水溶性或在水相中起始速率低之偶氮型起始劑; 5)反應溫度爲35-90°C; 6)所製得之水性樹脂之固含量爲4到15 重量％。 2. 如申請專利範圍第1項之乳化聚合方法，其中之偶氮型起始劑爲 2, 2'-偶氮雙異丁基精（2, 2匕 azobis (isobutyronitrile)，AIBN)、1，1、 偶氮雙環己院基骑（1，l1- azobis (cyclohexane carbonitrile，ACHC)或 4, 4'-偶氮雙異戊酸-4-膽(4, 4f- azobis- 4- cyanopentanoic acid，ACPA) 〇 3·如申請專利範圍第1項之乳化聚合方法，其中之偶氮型起始劑爲 2, 偶氮雙異丁基腈(AIBN)。 4·如申請專利範圍第1項之乳化聚合方法，其中之乳化劑爲聚乙烯 醇(PVA)及十二院基硫酸鈉（s〇dium dodecyl sulfate，SDS)。 5.如申請專利範圍第1到4項任一項之乳化聚合方法，其特徵爲先製 備較低固含量之水性樹脂，再以濃縮方式將水性樹脂固含量提高 到4到15重量％範圍。 i請先閲讀背面之注意事項再填寫本頁) 0 .裳 、1T 經濟部中央標準局員工消費合作社印製 524808 A8 B8 C8 D8 六、申請專利範圍 6. —種經乳化聚合方法製備之聚甲基丙烯酸酯均聚物水性樹脂，其 特徵爲：1)該聚甲基丙烯酸酯均聚物爲甲基丙烯酸-2-氫氧基乙 酯(HEMA)均聚物，或甲基丙烯酸氫氧基丙酯(HPMA)均聚物； 2)乳化聚合方法使用之乳化劑包含A及B，其中A爲聚乙烯醇 (PVA)或C6以上之脂肪醇，B爲烷基硫酸鹽、烷基磺酸鹽、或烷 基苯磺酸鹽等陰離子型界面活性劑;3)乳化聚合方法使用之起始 劑爲低/Jc溶性或在水相中起始速率低之偶氮型起始劑;4)該聚甲 基丙烯酸酯均聚物水性樹脂之固含量爲4到15重量％。 7. 如申請專利範圍第6項之聚甲基丙烯酸酯均聚物水性樹脂，其中 之偶氮型起始劑爲2,广偶氮雙異丁基月青（AIBN)、1，Γ-偶氮雙環 己院基腈（ACHC)或4,4·-偶氮雙異戊酸-4-腈(ACPA)。 8·如申請專利範圍第6項之聚甲基丙嫌酸酯均聚物水性樹脂，其中 之偶氮型起始劑爲2, 2'-偶氮雙異丁基腈（ΑΙΒΝ) 〇 9.如申請專利範圍第6項之聚甲基丙烯酸酯均聚物水性樹脂，其中 之乳化劑爲聚乙稀醇(PVA)及十二院基硫酸鈉（sodiumdodecyl sulfate，SDS)〇 10·如申請專利範圍第6到9項任一項之聚甲基丙燦酸酯均聚物水性 樹脂，其特徵爲先製備較低固含量之水性樹脂，再以濃縮方式將 水性樹脂固含量提高到4到15重量％範圍。 (請先閱讀背面之注意事項再填寫本頁) -裝. 線- 2524808 ί Bulletin 丨 A8 Β8 C8 D8 a VI-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs and applying for a patent scope 1. A method of emulsification polymerization for preparing a polymethacrylate homopolymer water-based resin, which is characterized by: 1) Use water as the carrier; 2) The monomer used is 2-Hydroxyethyl Methacrylate (HEMA) or Hydroxy Propyl Methacrylate (HPMA); 3) The emulsifier used contains A And B, where A is a polyvinyl alcohol (PVA) or a fatty alcohol of C6 or higher, and B is a calcined sulfate, a sulfonate, or an alkylbenzene sulfonate anionic surfactant; 4) from the time of use The initiator is an azo-type initiator with low water solubility or a low onset rate in the aqueous phase; 5) The reaction temperature is 35-90 ° C; 6) The solid content of the obtained aqueous resin is 4 to 15 weight %. 2. For example, the emulsification polymerization method in the scope of the patent application, wherein the azo-type initiator is 2, 2'-azobisisobutyl fine (2, 2 azobis (isobutyronitrile), AIBN), 1, 1. Cyclocarbonitrile (ACHC) or 4, 4'-azobisisovalerate 4-chol (4, 4f-azobis- 4-cyanopentanoic acid, ACPA) ) 〇3. The method of emulsification polymerization according to item 1 of the scope of patent application, wherein the azo-type initiator is 2, azobisisobutylnitrile (AIBN). 4. The method of emulsification polymerization according to item 1 of the scope of patent application Method, wherein the emulsifier is polyvinyl alcohol (PVA) and sodium dodecyl sulfate (SDS). 5. For the emulsification polymerization method according to any one of the claims 1 to 4, The feature is to prepare a low-solid water-based resin first, and then increase the solid content of the water-based resin to the range of 4 to 15% by weight. I Please read the precautions on the back before filling this page) 0. Clothes, 1T Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 524808 A8 B8 C8 D8 6. Scope of Patent Application 6. —Emulsified Polymerization The polymethacrylate homopolymer aqueous resin prepared by the method is characterized in that: 1) the polymethacrylate homopolymer is a 2-hydroxyoxyethyl methacrylate (HEMA) homopolymer, or Hydroxypropyl acrylate (HPMA) homopolymer; 2) The emulsifier used in the emulsion polymerization method includes A and B, where A is polyvinyl alcohol (PVA) or a fatty alcohol of C6 or higher, and B is an alkyl sulfate , Alkyl sulfonate, or alkyl benzene sulfonate and other anionic surfactants; 3) The emulsifier polymerization method uses a starting agent with low / Jc solubility or low starting rate in the aqueous phase. Starter; 4) The polymethacrylate homopolymer aqueous resin has a solid content of 4 to 15% by weight. 7. For example, the polymethacrylate homopolymer water-based resin in the scope of the patent application, wherein the azo-type initiator is 2, azobisisobutyl moon blue (AIBN), 1, Γ-couple Azobiscyclohexylnitrile (ACHC) or 4,4 · -azobisisovaleric acid-4-nitrile (ACPA). 8. The polymethylpropionate homopolymer water-based resin according to item 6 of the application, wherein the azo-type initiator is 2, 2'-azobisisobutylnitrile (ΑΙΒΝ) 〇9. For example, the polymethacrylate homopolymer water-based resin in item 6 of the patent application, where the emulsifier is polyvinyl alcohol (PVA) and sodium dodecyl sulfate (SDS). The polymethylpropionate homopolymer water-based resin according to any one of items 6 to 9, which is characterized by first preparing a low-solid water-based resin, and then concentrating the water-based resin solid content to 4 to 15 Weight% range. (Please read the notes on the back before filling out this page) -Packing. Thread-2
TW85109006A 1996-07-22 1996-07-22 Water-borne resin compositions of polymethacrylates possessing hydrophilic pendant groups TW524808B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW85109006A TW524808B (en) 1996-07-22 1996-07-22 Water-borne resin compositions of polymethacrylates possessing hydrophilic pendant groups

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW85109006A TW524808B (en) 1996-07-22 1996-07-22 Water-borne resin compositions of polymethacrylates possessing hydrophilic pendant groups

Publications (1)

Publication Number Publication Date
TW524808B true TW524808B (en) 2003-03-21

Family

ID=28450358

Family Applications (1)

Application Number Title Priority Date Filing Date
TW85109006A TW524808B (en) 1996-07-22 1996-07-22 Water-borne resin compositions of polymethacrylates possessing hydrophilic pendant groups

Country Status (1)

Country Link
TW (1) TW524808B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130303693A1 (en) * 2006-04-03 2013-11-14 Stepan Company Substituted alkoxylated phenols and branched sulfates for use in emulsion polymer latexes
US10619888B2 (en) 2016-03-02 2020-04-14 Watlow Electric Manufacturing Company Heater bundle for adaptive control and method of reducing current leakage

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130303693A1 (en) * 2006-04-03 2013-11-14 Stepan Company Substituted alkoxylated phenols and branched sulfates for use in emulsion polymer latexes
US10619888B2 (en) 2016-03-02 2020-04-14 Watlow Electric Manufacturing Company Heater bundle for adaptive control and method of reducing current leakage

Similar Documents

Publication Publication Date Title
RU2133756C1 (en) Emulsion polymer particle method of preparation thereof, composition and method of emulsion polymerization
Song et al. Cross-linked, monodisperse, micron-sized polystyrene particles by two-stage dispersion polymerization
US4029622A (en) Non-aqueous polymer dispersions of water-soluble monomers
JP2002506096A (en) Polymer composition
JPH05178912A (en) Production of cross-linked polymer particle
JPH05170845A (en) Fine organic polymer particle and its preparation
JPH0425282B2 (en)
JP5273311B2 (en) Additive for ceramic molding
JPS59199703A (en) Manufacture of emulsifier-free and protective colloid-free emulsion polymer
JPH07507350A (en) Surface treated absorbent polymer
TW524808B (en) Water-borne resin compositions of polymethacrylates possessing hydrophilic pendant groups
JPS61215602A (en) Production of polymer particle
US4640954A (en) Polymer suspension containing a water-soluble polymer suspended in an oil phase
JPS61215604A (en) Production of polymer particle
JPH04132705A (en) Production of hydrophilic fine grain
CN113583170B (en) Preparation method of micron-sized monodisperse polymethyl methacrylate crosslinked microspheres
JP2000501760A (en) Copolymers of carboxylic acids with polyolefinically unsaturated carboxylic acid derivatives and their use as thickeners and dispersants
JP2006137951A (en) Polymer particle and method of producing the same
JP2001518125A (en) Self-activating polymer particles having a narrow particle size distribution and method for producing the same
JP3666104B2 (en) Method for producing masterbatch comprising polymer particles in which fine polymer particles are dispersed
JPH028602B2 (en)
JP2021195521A (en) Molded body and method for manufacturing the same
JP3466301B2 (en) Method for producing monodisperse polystyrene-based particles
JPS63258913A (en) Hardening water-based resin dispersion
JPH11181003A (en) Production of polymer particle

Legal Events

Date Code Title Description
GD4A Issue of patent certificate for granted invention patent
MK4A Expiration of patent term of an invention patent