Synthesis of 2，6⁃monosubstituted bisphenol A isophthalaldehyde phenolic resin and its applications in reversible thermochromic composite NiBR film

doi:10.19491/j.issn.1001-9278.2024.04.006

Abstract

Abstract:

A 2，6⁃monosubstituted bisphenol⁃A （BPA）⁃isophthalaldehyde （IPD） oligomerized phenolic resin with a number⁃average molecular weight of 1.150×10³ g/mol and a polydispersion index of 1.004 was synthesized through microwave⁃assisted solution copolycondensation in an open system using BPA and potential biomass IPD as monomers. This potential biomass IPD has a low melting point， a weak π⁃π stacking interaction， and a slightly higher activity than terephthalaldehyde （TPD）. The structure of the as⁃synthesized phenolic resin was confirmed by ¹H⁃NMR， ¹³C⁃NMR， and FTIR. A reversible thermochromic composite Nickel⁃based butadiene rubber （NiBR） film was prepared by using the as⁃synthesized phenolic resin as a color developing agent. The results indicated that the flexibility of BPA⁃IPD and partially generated carboxyl end groups of IPD facilitated to generate low⁃ and high⁃temperature eutectic phases with lower latent heat due to a low melting point and a weak π⁃π stacking interaction of IPD. This improved the crystallization limit in the low temperature eutectic phase and color changing speed of the NiBR film and enhanced its compatibility with 1，4⁃high cis⁃NiBR and stability. The total color difference of the NiBR film was optimized to be around 85 at 12~37 ℃ through a formula. The absorption⁃scattering color depth difference of the NiBR film were approximately 20 and 45 at visible light range of 480~600 and 600~660 nm， respectively， and its color changing speed was 2.14 s^-1.

Key words: 2，6?monosubstituted bisphenol A isophthalaldehyde phenolic resin, reversible thermochromic, composite film, preparation

CLC Number:

TQ323

WANG Xiaohui, DONG Liming, GU Junjie, YAO Bing, CHEN Yan, LI Jing. Synthesis of 2，6⁃monosubstituted bisphenol A isophthalaldehyde phenolic resin and its applications in reversible thermochromic composite NiBR film[J]. China Plastics, 2024, 38(4): 32-39.

Figures/Tables 11

Fig.1. 1H⁃NMR and 13C⁃NMR the spectra of resin

Fig.2. FTIR curves of the resin

官能团/键	所在区域	振动类型	取代类型	波数/cm^-1	峰的强度（理论）
芳烃	特征区	ν（Ar—H）	—	3 085	W
		ν（C=C）	—	1 610	S
			—	1 597	S
			—	1 510	S
			—	1 461	W
	指纹区	δ（Ar—H）	—	1 275~960左右	W
		γ（Ar—H）	1， 2， 4⁃	757（孤立芳H）， 5个H	M
			1， 2， 4⁃	647（2个相邻H）， 10个H	S
			1， 3⁃	679（3个相邻H的中间位）， 3个H	VS
				562、551、530（3个相邻H的间隔位），裂分， 6个H	VS
				825（孤立芳H）， 3个H	M→S
			1， 4⁃	723左右（2个相邻H）， 4个H	VS
			1， 2， 3， 5⁃	845~640左右（孤立芳H）	×
OH	特征区	ν（O—H）	—	3 333	S， w
	指纹区	ν（C—O）	5H位	1 232	S
			8H位	1 217	S
			5H与8H位（共有）	1 176	S
			18H位、非端位	1 138	S
			2H， 1H位	1 099、1 093	W
			18H位、端位	1 083	S
		δ（O—H）	—	1 013	S
CHO （COOH）	特征区	C—H弯曲倍频与其伸缩的Fermi共振	—	2 722	M
		C—H弯曲倍频与其伸缩的Fermi共振	—	2 669	M
		ν（C=O）	—	1 731（酸）， 1 703（醛）	S
烷（羟）基	特征区	ν（C—H）	—	2 978（肩峰）	—
		δ_as ［C—H（OH）］	—	1 451左右（可能被包埋）	M
		δ_s ［C—H（OH）］	—	1 383	M
CH₃—C—CH₃	特征区	ν（C—H）	—	2 964	—
		δ_as （C—H）	—	1 444、1 434（分裂）	—
		δ_s （C—H）	—	1 361	—
	指纹区	ν（C—C）	—	1 250~800左右	W
	指纹区	ν（C—C）（异丙基肩峰）	—	1 295	—

Tab.1. Relationship of BPA⁃IPD’s infrared properties and structures

Fig.3. TG and DTG curves of the resin and composite film

Fig.4. DSC curves of the resin and composite film

相别	考察变量	实验组别	$Δ E$	$t$ /s	$Δ E$ /t/s^-1	结晶限/℃		$Δ$ H_m $/$ J·g^-1		$Δ$ H_c $/$ J·g^-1
分散相	CVL∶BPA⁃IPD	1∶1.0	57.0	42	1.43	26~37	37~48	11	62	17	53
		1∶1.5	87.2	40	2.18	23~36	36~46	8	61	16	42
		1∶2.0	83.4	39	2.14	23~36	36~46	6	54	13	33
		1∶2.5	78.2	42	1.86	22~35	35~45	5	50	13	31
		1∶3.0	72.8	48	1.52	21~34	35~44	5	43	11	29
		1∶3.5	67.7	50	1.35	20~34	35~44	4	38	10	28
	CVL∶（十六醇+十八醇）	1∶10	71.8	21	3.42	24~35	35~42	2	27	6	13
		1∶20	76.2	31	2.46	24~34	36~44	3	28	7	20
		1∶30	79.8	36	2.22	23~34	37~45	3	33	8	34
		1∶40	81.8	38	2.13	23~33	37~47	5	45	12	37
		1∶50	88.2	43	2.04	24~35	38~47	12	48	12	45
		1∶60	80.7	46	1.75	24~36	37~46	17	53	13	52
	十六醇∶十八醇	0.38∶0.00	81.9	25	3.28	—	35~39	—	106	—	100
		0.30∶0.08	86.3	32	2.70	22~32	36~41	2	53	14	39
		0.23∶0.15	91.6	43	2.13	23~34	37~44	13	46	16	41
		0.15∶0.23	87.0	37	2.35	26~38	39~46	4	48	15	37
		0.08∶0.30	82.5	28	2.95	37~43	43~47	2	71	16	58
		0.00∶0.38	72.1	17	4.24	—	44~49	—	98	—	105
连续相	CVL∶NiBR	1∶10	80.0	28	2.86	25~37	37~46	5	70	18	48
		1∶20	81.5	31	2.63	25~37	38~46	6	78	19	52
		1∶30	84.2	34	2.48	24~36	38~47	10	79	20	55
		1∶40	86.2	35	2.46	24~36	37~46	7	82	20	43
		1∶50	88.0	36	2.44	24~36	36~45	5	52	15	35
		1∶60	88.2	44	2.00	23~36	36~44	5	50	14	31

相别	考察变量	实验组别	$Δ E$	$t$ /s	$Δ E$ /t/s^-1	结晶限/℃		$Δ$ H_m $/$ J·g^-1		$Δ$ H_c $/$ J·g^-1
分散相	CVL∶BPA⁃IPD	1∶1.0	57.0	42	1.43	26~37	37~48	11	62	17	53
		1∶1.5	87.2	40	2.18	23~36	36~46	8	61	16	42
		1∶2.0	83.4	39	2.14	23~36	36~46	6	54	13	33
		1∶2.5	78.2	42	1.86	22~35	35~45	5	50	13	31
		1∶3.0	72.8	48	1.52	21~34	35~44	5	43	11	29
		1∶3.5	67.7	50	1.35	20~34	35~44	4	38	10	28
	CVL∶（十六醇+十八醇）	1∶10	71.8	21	3.42	24~35	35~42	2	27	6	13
		1∶20	76.2	31	2.46	24~34	36~44	3	28	7	20
		1∶30	79.8	36	2.22	23~34	37~45	3	33	8	34
		1∶40	81.8	38	2.13	23~33	37~47	5	45	12	37
		1∶50	88.2	43	2.04	24~35	38~47	12	48	12	45
		1∶60	80.7	46	1.75	24~36	37~46	17	53	13	52
	十六醇∶十八醇	0.38∶0.00	81.9	25	3.28	—	35~39	—	106	—	100
		0.30∶0.08	86.3	32	2.70	22~32	36~41	2	53	14	39
		0.23∶0.15	91.6	43	2.13	23~34	37~44	13	46	16	41
		0.15∶0.23	87.0	37	2.35	26~38	39~46	4	48	15	37
		0.08∶0.30	82.5	28	2.95	37~43	43~47	2	71	16	58
		0.00∶0.38	72.1	17	4.24	—	44~49	—	98	—	105
连续相	CVL∶NiBR	1∶10	80.0	28	2.86	25~37	37~46	5	70	18	48
		1∶20	81.5	31	2.63	25~37	38~46	6	78	19	52
		1∶30	84.2	34	2.48	24~36	38~47	10	79	20	55
		1∶40	86.2	35	2.46	24~36	37~46	7	82	20	43
		1∶50	88.0	36	2.44	24~36	36~45	5	52	15	35
		1∶60	88.2	44	2.00	23~36	36~44	5	50	14	31

Tab.2. Thermochromic properties of the composite films

Fig.5. Effect of process conditions on composite films’ ΔKS values

Fig.6. DSC cycle curves of phase transition of the composite film

Fig.7. Composite film’s morphology changes during cooling

Fig.8. Different stages’ physical photos of composite film’s thermochromic process

Fig.9. Co⁃crystallization’s main mechanisms of CVL， BPA⁃IPD and mixed alcohols at low temperature region

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