交联改性丙烯酸酯乳液及其在装饰纸上的应用研究

doi:10.3969/j.issn.0253-2417.2021.06.008

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (6): 57-66.doi: 10.3969/j.issn.0253-2417.2021.06.008

交联改性丙烯酸酯乳液及其在装饰纸上的应用研究

付高位¹^,²(), 冯旺龙¹^,², 王定坤¹^,², 陈日清¹^,*(), 王春鹏¹

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2020-11-26 出版日期:2021-12-28 发布日期:2021-12-31
通讯作者: 陈日清 E-mail:785849751@qq.com;michaelmao77@163.com
作者简介:陈日清, 副研究员, 硕士生导师, 主要从事生物基高分子材料研究; E-mail: michaelmao77@163.com
付高位(1993-), 河南周口人, 硕士生, 从事乳液聚合方面研究; E-mail: 785849751@qq.com
基金资助:
中央级公益性科研院所基本科研业务专项资金重点项目(CAFYBB2018ZB008)

Cross-linked Acrylic Emulsion and Its Application in Decorative Paper

Gaowei FU¹^,²(), Wanglong FENG¹^,², Dingkun WANG¹^,², Riqing CHEN¹^,*(), Chunpeng WANG¹

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2020-11-26 Online:2021-12-28 Published:2021-12-31
Contact: Riqing CHEN E-mail:785849751@qq.com;michaelmao77@163.com

摘要/Abstract

摘要：

以甲基丙烯酸乙酰乙酰氧基乙酯（AAEM）为交联单体，通过种子乳液半连续法制备了丙烯酸酯乳液型胶黏剂。利用红外光谱仪、差示扫描量热仪、热重分析仪、扫描电子显微镜、万能材料试验机等，考察了AAEM用量对丙烯酸酯乳液的聚合影响及在装饰纸上的应用研究。红外分析表明AAEM成功参与了乳液共聚反应。AAEM改性后的丙烯酸酯乳液粒径和黏度分别达到90 nm和21.0 mPa·s以下，单体转化率高达97%以上；改性后的乳胶膜交联度最高达到90.61%。同时，AAEM改性还提高了乳胶膜的热稳定性和耐水性能。胶膜纸的浸渍试验验证了丙烯酸酯乳液成功浸渍到纸张内部，极大提高了装饰纸的机械性能、表面胶合强度、表面耐水性能。浸渍后的胶膜纸挥发分的量和预固化度基本维持在12%~15%和62%~65%，其拉伸强度和断裂伸长率最高分别达到25 MPa和26.9%，同比浸渍前分别提高了13 MPa和25.1个百分点，接触角最高达113°，表面胶合强度达到0.826 MPa。

关键词: 乳液聚合, 后交联单体, AAEM, 丙烯酸酯, 胶膜纸

Abstract:

The acrylic emulsion adhesive was prepared by semi-continuous seed emulsion method with using acetoacetoxyethyl methacrylate(AAEM) as the crosslinking agent. The effects of AAEM amount on acrylic emulsion polymerization and its application as an adhesive for the decorative paper were investigated by infrared spectrometer, differential scanning calorimeter, thermogravimetric analyzer, scanning electron microscope, universal material testing machine, etc.. The IR results showed that AAEM was successfully participated in the emulsion copolymerization reaction. The particle size and viscosity of the acrylate emulsion modified by AAEM were below 90 nm and 21.0 mPa·s, respectively, and the monomer conversion rate was above 97% and the crosslinking degree of the film obtained from acrytic emulsion reached 90.61%. The modification of AAEM improved the crosslinking degree, thermal stability and water resistance of the obtained acrylate polymer. The impregnation test of the impregnated paper verified that the acrylic emulsion was successfully impregnated into the decorative papers, and greatly improved their mechanical properties, surface bonding strength, surface water resistance. The volatile content and pre-curing degree of the impregnated paper prepared by cross-linked acrylic emulsion, basically maintained at 12%-15% and 62%-65% when it was dipped; the tensile strength and elongation at break were up to 25 MPa and 26.9%, respectively, which were increased by 13 MPa and 25.1% while compared with that of the controlled sample. And the maximum contact angle was 113° and the surface bonding strength reached 0.826 MPa.

Key words: emulsion polymerization, crosslinking monomer, AAEM, acrylic, thermosetting resins paper

中图分类号:

付高位, 冯旺龙, 王定坤, 陈日清, 王春鹏. 交联改性丙烯酸酯乳液及其在装饰纸上的应用研究[J]. 林产化学与工业, 2021, 41(6): 57-66.

Gaowei FU, Wanglong FENG, Dingkun WANG, Riqing CHEN, Chunpeng WANG. Cross-linked Acrylic Emulsion and Its Application in Decorative Paper[J]. Chemistry and Industry of Forest Products, 2021, 41(6): 57-66.

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参考文献 17

1	付纪磊, 王广森, 郭明辉, 等. 国内浸渍胶膜纸及饰面人造板行业前景展望[J]. 世界林业研究, 2014, 27 (3): 62- 66.
	FU J L , WANG G S , GUO M H , et al. Prospects of domestic impregnated film paper and facing wood-based panel industry[J]. World Forestry Research, 2014, 27 (3): 62- 66.
2	姜振凡. 高性能低压短周期浸渍纸用树脂的研制[D]. 长沙: 中南林业科技大学, 2012.
	JIANG Z F. Development of high performance low pressure short cycle impregnated paper resin[D]. Changsha: Central South University of Forestry and Technology, 2012.
3	王荣兴, 张祖新, 陈日清, 等. 三(2-羟乙基)异氰尿酸酯改性三聚氰胺甲醛浸渍树脂的机理研究[J]. 林产化学与工业, 2018, 38 (2): 126- 132. doi: 10.3969/j.issn.0253-2417.2018.02.017
	WANG R X , ZHANG Z X , CHEN R Q , et al. Synthesis mechanism of tris (2-hydroxyethyl) isocyanate modified melamine formaldehyde impregnated resin[J]. Chemistry and Industry of Forest Products, 2018, 38 (2): 126- 132. doi: 10.3969/j.issn.0253-2417.2018.02.017
4	郭俊杰, 张宏元. 乳液聚合技术现状及应用前景[J]. 粘接, 2006, 27 (1): 44- 47. doi: 10.3969/j.issn.1001-5922.2006.01.017
	GUO J J , ZHANG H Y . Present situation and application prospects of technology in emulsion polymerization[J]. Adhesion, 2006, 27 (1): 44- 47. doi: 10.3969/j.issn.1001-5922.2006.01.017
5	张祖新, 付高位, 陈日清, 等. 丙烯酸酯后交联乳液的性能研究[J]. 中国胶粘剂, 2019, 28 (3): 6- 9, 14.
	ZHANG Z X , FU G W , CHEN R Q , et al. Study on properties of acrylate post-crosslinking emulsion[J]. China Adhesives, 2019, 28 (3): 6- 9, 14.
6	曹辉波, 何静. 甲基丙烯酸羟酯类单体改性苯丙乳液在纸张中的应用[J]. 山西大学学报(自然科学版), 2011, 34 (3): 458- 463.
	CAO H B , HE J . Application of the hydroxyethyl methacrylate monomer modified styrene-acrylic emulsion in the paper[J]. Journal of Shanxi University (Natural Science Edition), 2011, 34 (3): 458- 463.
7	杜方凯, 李梦汝. 甲基丙烯酸乙酰乙酰氧基乙酯改性丙烯酸酯乳液压敏胶的制备及其性能[J]. 化工新型材料, 2019, 47 (8): 74- 79.
	DU F K , LI M R . Synthesis and property of AAEM modified acrylate latex PSA[J]. New Chemical Materials, 2019, 47 (8): 74- 79.
8	雷亮, 夏正斌, 邢俊恒, 等. 乙酰乙酰基丙烯酸酯聚合物乳液的合成及室温交联改性[J]. 高校化学工程学报, 2014, (3): 561- 566. doi: 10.3969/j.issn.1003-9015.2014.03.020
	LEI L , XIA Z B , XING J H , et al. Synthesis and ambient crosslinking of acetoacetate acrylate polymer emulsion[J]. Journal of Chemical Engineering of Chinese Universities, 2014, (3): 561- 566. doi: 10.3969/j.issn.1003-9015.2014.03.020
9	ZOLLER A , KOCKLER K B , ROLLET M , et al. A complete kinetic study of a versatile functional monomer: Acetoacetoxyethyl methacrylate (AAEMA)[J]. Polymer Chemistry, 2016, 7, 5518- 5526. doi: 10.1039/C6PY01115B
10	BERTOLIN M , ZECCA M , FAVERO G , et al. High-yield γ-ray-induced polymerization of bis-2-acetoacetoxyethyl methacrylate copper.II[J]. Journal of Applied Polymer Science, 2015, 65 (11): 2201- 2207.
11	国家林业局. LY/T 1143-2006饰面用浸渍胶膜纸[S]. 北京: 中国标准出版社, 2006.
	State Forestry Administration. LY/T 1143-2006 Impregnated thermosetting resins paper for decoration[S]. Beijing: Standards Press of China, 2006.
12	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. GB/T 17657-2013人造板及饰面人造板理化性能试验方法[S]. 北京: 中国标准出版社, 2013.
	General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. Standardization Administration. GB/T 17657-2013 Test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels[S]. Beijing: Standards Press of China, 2013.
13	SCHLAAD H , KRASIA T , ANTONIETTI M . Superhelices of poly[J]. Journal of the American Chemical Society, 2004, 126 (36): 11307- 11310. doi: 10.1021/ja047858z
14	KNOEVENAGEL E . Condensation von malonsure mit aromatischen aldehyden durch ammoniak und amine[J]. European Journal of Inorganic Chemistry, 2010, 31 (3): 2596- 2619.
15	MOSZNER N , ZEUNER F , SALZ U , et al. Reaction behaviour of monomeric β-ketoesters[J]. Polymer Bulletin, 1994, 33 (1): 43- 49. doi: 10.1007/BF00313472
16	SANCHEZ-SANCHEZ A , ARBE A , KOHLBRECHER J , et al. Efficient synthesis of single-chain globules mimicking the morphology and polymerase activity of metalloenzymes[J]. Macromolecular Rapid Communications, 2015, 36 (17): 1592- 1597.
17	池永亮. 浅析浸渍胶膜纸生产技术及其生产质量控制[J]. 中国人造板, 2010, 17 (8): 24- 29.
	CHI Y L . Processing technology and quality control of impregnated paper production[J]. China Wood-Based Panels, 2010, 17 (8): 24- 29.

实验组 experiment	AAEM质量分数/% mass fraction of AAEM	单体转化率/% conversion rate of monomer	乳胶粒粒径/nm size of emulsion particle	多分散系数 polydispersity index(PDI)	乳液黏度/(mPa·s) viscosity of emulsion	乳液凝胶率/% gel rate of emulsion
Late 1	0	97.4	86	0.031	23.0	0
Late 2	0.5	98.1	81	0.045	18.5	0
Late 3	1	97.7	83	0.022	18.5	0
Late 4	3	98.3	85	0.031	19.5	0
Late 5	5	97.9	88	0.041	20.8	0
Late 6	10	97.2	90	0.040	21.0	0.57

实验组 experiment	24 h吸水率/% water absorption at 24 h		48 h吸水率/% water absorption at 48 h		72 h吸水率/% water absorption at 72 h
实验组 experiment	室温膜 room temperature film	热处理膜 heat treatment film	室温膜 room temperature film	热处理膜 heat treatment film	室温膜 room temperature film	热处理膜 heat treatment film
Late 1	6.05	4.63	8.99	7.80	11.58	10.43
Late 2	4.73	3.34	5.45	5.00	9.09	6.84
Late 3	4.69	3.77	5.63	6.20	11.01	8.42
Late 4	8.43	5.68	12.86	8.06	18.14	10.95
Late 5	5.86	4.15	7.19	5.91	8.36	8.36
Late 6	7.93	3.07	10.98	5.00	15.24	6.36

实验组 experiment	T_g/℃	初始分解温度/℃ initial decomposition temperature	分解最快温度/℃ fastest decomposition temperature	残留质量/% residual mass
Late 1	16.2	373.4	400.2	0.95
Late 2	14.2	371.5	398.8	0.44
Late 3	14.5	373.7	398.8	0.97
Late 4	17.0	382.8	406.1	2.07
Late 5	17.1	394.3	416.4	2.65
Late 6	14.2	394.6	420.8	1.10

样品 sample	拉伸强度/MPa tensile strength	断裂伸长率/% elongation at break
原纸base paper	12	1.8
Late 1	14	7.8
Late 2	18	15.9
Late 3	20	17.1
Late 4	21	16.0
Late 5	23	19.0
Late 6	25	26.9

热压温度/℃ hot pressing temperature	热压压力/MPa hot pressing pressure	热压时间/s hot pressing time	表面胶合强度/MPa bonding strength
120	1.0	60	0.536
140	1.0	60	0.746
160	1.0	60	0.826
140	1.0	90	0.753
140	1.0	120	0.730
120	0.5	60	0.486
120	1.5	60	0.695

交联改性丙烯酸酯乳液及其在装饰纸上的应用研究

Cross-linked Acrylic Emulsion and Its Application in Decorative Paper

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