Effect of silane coupling agent MPS on crosslinking structure and shear orientation ability of SiO2-polyacrylate composite particles
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摘要: 为了探究γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)对SiO2-聚丙烯酸酯(PAcr)复合微球结构与性能的影响，在丙烯酸丁酯与甲基丙烯酸甲酯的自由基悬浮共聚合体系中加入MPS、MPS偶联改性的SiO2(MPS-SiO2)纳米粒子或MPS偶联改性SiO2纳米粒子的原始分散液，分别考察了非偶联MPS的量、偶联MPS的量、偶联与非偶联MPS的相对含量对SiO2-PAcr复合微球交联程度和交联结构的作用规律，并进一步对比了具有不同交联结构复合微球的剪切取向能力。通过TEM观察发现，非偶联MPS会水解自缩聚产生直径约6 nm的颗粒（即MPS水解颗粒），表面带有可聚合双键，能起到交联作用。MPS偶联改性SiO2纳米粒子原始分散液除含有MPS-SiO2纳米粒子外，还含有MPS水解颗粒，因而能构筑双重交联结构。具有这种双重交联结构的复合微球在HAAKE转矩流变仪中经熔融剪切可形成平均长径比高达12.0的取向体，而单独以MPS水解颗粒或MPS-SiO2纳米粒子为交联点的微球经相同的熔融剪切过程只能形成平均长径比分别为9.1和8.8的取向体。这表明，偶联和非偶联MPS所构造的两种不同尺度的交联结构对SiO2-PAcr复合微球剪切取向能力的提高有着显著的协同作用。
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关键词:
- 复合微球 /
- γ-甲基丙烯酰氧基丙基三甲氧基硅烷 /
- 双重交联 /
- 剪切取向 /
- 协同作用
Abstract: In order to reveal the effect of γ-methacryloxypropyl trimethoxysilane (MPS) on the structure and property of SiO2-polyacrylate (PAcr) composite particles, MPS, MPS modified SiO2 (MPS-SiO2) nanoparticles, and the raw dispersions obtained from the modification of SiO2 nanoparticles with MPS were used as the additives in the radical suspension copolymerization of butyl acrylate and methyl methacrylate. The influence of the amount of coupled and uncoupled MPS and the ratio of coupled MPS to uncoupled MPS on the crosslinking degree and crosslinking structure of SiO2-PAcr composite particles was investigated, and the shear orientation abilities of the composite particles with different crosslinking structures were compared. TEM observation shows that some irregular particles with diameter at about 6 nm are formed by the hydrolytic condensation of uncoupled MPS (i.e. MPS condensed particles). The MPS condensed particles can act as the crosslinking points owing to the double bonds on their surface. By adding the raw dispersions from MPS modification of SiO2 nanoparticles, dual-crosslinking structure can be formed in the SiO2-PAcr composite particles because both coupled and uncoupled MPS are included in the polymerization system. The as-prepared dual-crosslinked particles can be deformed into the orientated structure with a high aspect ratio of 12.0 in HAAKE torque rheometer. However, the aspect ratio after the same shear orientation process can only reach 8.8 and 9.1 with coupled or uncoupled MPS as additives, respectively. The coupled and uncoupled MPS can lead to two different kinds of crosslinking structures, which improves the shear orientation ability of SiO2-PAcr composite particles synergistically. -
图 1 MPSuncoupled-SiO2-PAcr复合微球在二甲基甲酰胺（DMF）中60 ℃时的形态及投影面积随时间的变化
Figure 1. Time-dependent change of projection area ratio and morphology of MPSuncoupled-SiO2-PAcr composite particles in dimethyl formamide(DMF) at 60 ℃
图 2 以γ-甲基丙烯酰氧基丙基三甲氧基硅烷（MPS）-SiO2纳米粒子或其未经离心的原始分散液为添加剂时，MPS用量(MPS与SiO2质量比)与复合微球凝胶率(Gc)、平衡溶胀比(Q)之间的关系(SiO2用量为4 g)
Figure 2. Effect of γ-methacryloxypropyl trimethoxysilane(MPS) content (MPS:SiO2 mass ratio) on gel rate (Gc) and equilibrium swelling ratio (Q) of composite particles prepared using MPS modified SiO2 nanoparticle or its raw dispersions as additive (mass of SiO2 is 4 g)
图 3 MPS改性SiO2原始分散液中偶联MPS含量与总MPS含量的关系(a区域中竖线长度=非偶联MPS含量)
Figure 3. Relationship curve between coupled MPS content and total MPS content in the raw dispersions obtained from modification of SiO2 nanoparticles with MPS (lengths of vertical lines in area a = Uncoupled MPS content)
图 4 不添加SiO2纳米粒子时，添加不同量MPS(MPS与MMA和BA单体质量比) 时，MPS-PAcr复合微球投影面积随时间的变化
Figure 4. Time-dependent projection area ratio curves of MPS-PAcr composite particles prepared at different MPS content without SiO2 (mass ratio of MPS to monomers of MMA and BA)
图 5 未添加SiO2纳米粒子时，不同MPS用量(MPS与MMA和BA单体质量比) MPS-PAcr复合微球的平衡溶胀比(Q)和溶胀平衡时间(teq)
Figure 5. Equilibrium swelling ratio (Q) and equilibrium swelling time (teq) of MPS-PAcr composite particles prepared at different MPS contents without SiO2 (mass ratio of MPS to monomers of MMA and BA)
图 6 不同SiO2用量(SiO2与MMA和BA单体质量比) MPSuncoupled-SiO2-PAcr复合微球投影面积随溶胀时间变化曲线(MPS与单体的质量比为0.2%)
Figure 6. Time-dependent projection area ratio curves of MPSuncoupled-SiO2-PAcr composite particles prepared at different SiO2 contents (mass ratio of SiO2 to monomers of MMA and BA, MPS:Monomers mass ratio=0.2%)
图 7 不同SiO2用量(SiO2与MMA和BA单体质量比) MPSuncoupled-SiO2-PAcr复合微球的平衡溶胀比(Q)与溶胀平衡时间(teq)(MPS与单体的质量比为0.2%)
Figure 7. Equilibrium swelling ratio (Q) and equilibrium swelling time (teq) of MPSuncoupled-SiO2-PAcr composite particles prepared at different SiO2 contents (mass ratio of SiO2 to monomers of MMA and BA, MPS : Monomers mass ratio=0.2%)
图 8 SiO2纳米粒子(a)、MPS偶联改性SiO2原始分散液((b)、(c))和MPS水解产物的TEM图像(d) ((c)为(b)中虚线框所示区域的放大图)
Figure 8. TEM images for SiO2 nanoparticles (a), raw dispersions from MPS modification of SiO2 ((b), (c)) and MPS hydrolyzed polycondensate (d) ((c) is the dashed line marked area in (b))
图 9 MPS、MPS水解颗粒、MPS-SiO2离心上清液干燥物和原始SiO2的FTIR图谱
Figure 9. FTIR spectra of MPS，MPS hydrolyzed polycondensate，dry matter of MPS-SiO2 centrifugal upper layer and pristine SiO2
图 10 MPS-PAcr复合微球(a)、MPScoupled-SiO2-PAcr复合微球(b)、MPSuncoupled-SiO2-PAcr复合微球(c)与聚甲基丙烯酸甲酯(PMMA)在HAAKE转矩流变仪中熔融剪切共混产物切片的TEM图像及图中取向体的长径比统计结果(d)
Figure 10. TEM images of MPS-PAcr(a), MPScoupled-SiO2-PAcr(b) and MPSuncoupled-SiO2-PAcr(c) composite particles after shear orientation in polymethyl methacrylate(PMMA) matrix and aspect ratio distributions of MPS-PAcr, MPScoupled-SiO2-PAcr and MPSuncoupled-SiO2-PAcr(d)
图 11 MPScoupled-SiO2-PAcr复合微球(a)、MPSuncoupled-SiO2-PAcr复合微球(b)和MPS-PAcr复合微球(c)可能的内部交联结构
Figure 11. Proposed network structures in MPScoupled-SiO2-PAcr (a), MPSuncoupled-SiO2-PAcr (b) and MPS-PAcr (c) composite particles
表 1 制备SiO2-聚丙烯酸酯(PAcr)复合微球的基础配方(g)
Table 1. Basic recipe for the fabrication of SiO2- polyacrylate(PAcr) composite particles (g)
MMA BA BPO H2O Mg(OH)2 SDS NaNO2 40 40 1.5 200 8.7 0.075 0.15 Notes: MMA—Methyl methacrylate; BA—Butyl acrylate; BPO—Benzoyl peroxide; SDS—Sodium dodecyl sulfonate. 
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